CN108499370A - A kind of preparation method of ion blotting blend film - Google Patents
A kind of preparation method of ion blotting blend film Download PDFInfo
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- CN108499370A CN108499370A CN201810333720.8A CN201810333720A CN108499370A CN 108499370 A CN108499370 A CN 108499370A CN 201810333720 A CN201810333720 A CN 201810333720A CN 108499370 A CN108499370 A CN 108499370A
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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
- B01D71/80—Block polymers
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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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/42—Ion-exchange membranes
Abstract
The present invention relates to a kind of preparation methods of ion blotting blend film, include the following steps：(1) synthesis of Macromolecular chain transfer agent：It is synthesized in scheduled ratio in thermal initiator using methyl methacrylate and RAFT reagents；(2) synthesis of amphipathic block functional polymer：The Macromolecular chain transfer agent synthesis that will be synthesized in 4 vinylpyridines, thermal initiator and step (1)；(3) synthesis of template ion polymer complex；(4) casting film：By in step (3) template ion polymer complex and film matrix in scheduled ratio dissolve in a solvent stirring the predetermined time to be uniformly mixed obtain casting solution, by casting solution remove bubble after casting film；(5) it elutes.Present invention hydrophilic block in film forming procedure can move quickly into the surface of film, will not be embedded by PVDF because of template ion too deep without easily eluting, and generate more binding sites on the surface of film, increase ion blotting blend film adsorptive selectivity and adsorption capacity.
Description
Technical field
The invention belongs to ionic imprinting technique fields, and in particular to a kind of preparation method of ion blotting blend film.
Background technology
Molecule (ion) blotting membrane refers to a kind of film for including or being made of molecularly imprinted polymer, by polymer to mould
The memory recognition performance of plate molecule achievees the purpose that molecular recognition, molecule space recognition capability are strong, it can be achieved that highly selective point
From；Basic ideas are that microsphere is added in polymerisation medium, remove microsphere after film forming, trace polymerization layer reticular structure
In be left with the hole to match with microsphere size, there are phase interactions between the blotting membrane and microsphere of generation
With when using it for the mixture that separation microsphere is constituted with other materials, blotting membrane can recognize that microsphere, to have
Effect ground detaches object from mixture.
Currently, it is most attraction that molecular imprinting technology is combined with membrane preparation technology to the molecular engram blend film generated
One of research, molecular engram process is generally required in the prior art forms and microsphere size using after cross-linking agents
Identify target microsphere in turn in the hole to match.And prepare trace blend film usually will appear template molecule (from
Son) envelope matrix embedding it is too deep without easily eluting the phenomenon that, trace blend film adsorption capacity and absorption can be substantially reduced in this way
Rate.
In conclusion that it is urgent to provide a kind of structural behaviours is stable, is not easy to peel off, adsorption capacity height and the rate of adsorption it is fast from
The preparation method of sub- trace blend film.
Invention content
That the object of the present invention is to provide a kind of structural behaviours is stable, be not easy to peel off, and adsorption capacity height and the rate of adsorption are fast
The preparation method of ion blotting blend film.
Above-mentioned purpose is to be achieved through the following technical solutions：A kind of preparation method of ion blotting blend film, including it is as follows
Step：
(1) synthesis of Macromolecular chain transfer agent：By methyl methacrylate, RAFT reagents and thermal initiator by scheduled
Ratio is added in reactor, is sealed after addition solvent and is reacted under a shielding gas, precipitation filtering is carried out after the completion of reaction,
Obtained solid product is dried to constant weight；
(2) synthesis of amphipathic block functional polymer：It will be closed in 4-vinylpridine, thermal initiator and step (1)
At Macromolecular chain transfer agent be added by scheduled ratio to reactor, be added after solvent seal and be reacted, react completion
After carry out precipitation filtering, obtained solid product is dried to constant weight；
(3) synthesis of template ion-polymer complex：The amphipathic block functional polymer that will be synthesized in step (2)
It is dispersed in the container equipped with template ion aqueous solution, then sealing reaction is filtered after reacting fully, is washed with deionized water
It washs and is freeze-dried；
(4) casting film：By in step (3) template ion-polymer complex and film matrix be dissolved in scheduled ratio
The stirring predetermined time obtains casting solution to uniformly mixed in solvent, and casting solution is stood predetermined time removing bubble, then will be cast
Film liquid pours into film-forming plates, and casting solution is laid into uniform film, by the film immerse rapidly predetermined temperature go from
Film solidification is carried out in sub- water-bath, washing film removes residual solvent；
(5) it elutes：Using the membrane elution template ion prepared in eluant, eluent rinsing step (4), the ion blotting is obtained
Blend film.
Amphipathic block functional polymer prepared by the present invention, including A blocks and B block, wherein A blocks are hydrophobic chain
Section, has and film matrix has fine compatibility and the polymer containing unsaturated bond, to tangle, fix with film basis material；B
Block is hydrophilic segment, is had and metal ion binding capacity and the hydrophilic polymer containing unsaturated bond.A in the present invention
The monomer of block is methyl methacrylate (MMA), and the monomer of B block is 4-vinylpridine (4VP).
It is polymerize first with RAFT reagents using MMA in preparation process, then with obtained Macromolecular chain transfer agent
PMMA-RAFT is polymerize as Macromolecular chain transfer agent with 4VP, and amphipathic nature block polymer polymethylacrylic acid is finally obtained
Methyl esters-P4VP writes a Chinese character in simplified form PMMA-b-P4VP, is combined with template ion using PMMA-b-P4VP functional polymers
Metal organic complexes are formed, solvent is reused, if dimethylacetylamide (DMAc) is by this compound and Kynoar
(PVDF) it is blended, is finally that coagulating bath prepares ion blotting blending with non-solvent induction phase separation method (NIPS) to ionized water
Film.
In film matrix solidification process, amphipathic block functional polymer migrates (also referred to as surface segregation) to film surface, makes
Metal form is moved to the surface of film, and the holes 3D with metal form complementation are formed in cured film surface after elution.At
The hydrophilic block of functional polymer can move quickly into the surface of film by surface segregation in membrane process, will not be because of template ion
By the too deep without easily eluting of PVDF embeddings, meanwhile, there are more hydrophilic blocks on the surface of film to generate more combine
Site can make object ion occur quickly to combine with film surface binding site, eventually lead to ion blotting blend film and selectively inhale
Attached capacity increases performance enhancement, and adsorption rate is fast, service life enhancing.Again, the membrane structure formed in this way, function
Hydrophobic chain in polymer can be fully closely wound with film matrix, and it is made to be difficult to fall off from trace film surface.Ion prints
Mark blend film has broken away from the limitation that crosslinking agent is used in traditional printing process, and in addition the synthesis of amphipathic block functional polymer can
The length of B block is controlled by controlling the reaction time, improves ion blotting blend film adsorption capacity and the rate of adsorption.
Preferably, further technical solution is：In the step (1) and step (2), the RAFT reagents, heat are drawn
It is respectively three thioesters, azodiisobutyronitrile and N,N-dimethylformamide to send out agent and solvent.
Further technical solution is：Film matrix and solvent in the step (4) are respectively Kynoar and N, N-
Dimethylacetylamide.
Kynoar (PVDF) is semicrystalline strong-hydrophobicity polymer, can be cured rapidly in water, and film-formation result is good,
Kynoar can be tangled with PMMA, fixed well simultaneously, and ion blotting blend film stable structure, imprinted material is not easy to take off
It falls.
Further, the template ion is Pt (IV), and template ion solution is platinum acid chloride solution.
Further technical solution is：Eluant, eluent in the step (5) is the mixed solution of thiocarbamide and hydrochloric acid.Experiment card
Bright, the thiocarbamide of suitable concentration and the mixed solution of hydrochloric acid are good to template Pt (IV) ion elution effects.
Further technical solution is：The methyl methacrylate uses the preceding flash layer through being filled with alkali alumina
It analyses column and removes polymerization inhibitor, and be sealed at 2 DEG C and be kept in dark place；The azodiisobutyronitrile is recrystallized using preceding in absolute ethyl alcohol
Three times, it is sealed at 2 DEG C and is kept in dark place；The Kynoar is removed water for 24 hours using preceding be dried in vacuo at 90 DEG C.
Further technical solution is：Concrete technology in the step (1) is：By 15.0g methyl methacrylates,
Tri- thioesters reagents of 0.1g and 0.2g azodiisobutyronitriles are dissolved in 36.9mL n,N-Dimethylformamide, by above-mentioned mixed solution
It is added in reactor, then seals, after deaerating and being full of nitrogen in the reactor, in 70 DEG C of pre- hot oil bath and keep continuous
It stirs reaction to mix 6 hours, is cooled to room temperature, the mixture after reaction is diluted with tetrahydrofuran, and excessive after the completion of reaction
It precipitates in low-temp methanol three times, finally, obtained Macromolecular chain transfer agent is dried in vacuo 24 hours at 40 DEG C.
Further technical solution is：Concrete technology in the step (2) is：Take the big of the middle synthesis of 2.0g steps (1)
Molecular chain transfer agent and 3.0g 4-vinylpridines and 1mg azodiisobutyronitriles are dissolved in 12.3mL dimethylformamides；
Above-mentioned mixed solution is added in reactor, is then sealed, after deaerating and being full of nitrogen in the reactor, 70 DEG C of pre- deep fat
In bath and holding is continuously stirred reaction and is mixed 6 hours, is cooled to room temperature after the completion of reaction, and the mixture dichloromethane after reaction is dilute
It releases, and is precipitated three times in excessive low-temp methanol；Finally, by the amphipathic block functional polymer of acquisition at 40 DEG C vacuum
It is 24 hours dry.
Further technical solution is：Concrete technology in the step (3) is：Take amphipathic block functional polymer
4.00g be dispersed in 100mL contain 50mg templates platinum (IV) ion, pH=0.5 ± 0.1 solution in, then sealing and at 25 DEG C
Under keep constant stirring 24 hours, then filtering gained mixture, be washed with deionized and be freeze-dried.
Further technical solution is：Concrete technology in the step (4) and step (5) is：It will be prepared in step (3)
The dissolving of template ion-polymer complex and Kynoar press 3:10 ratio is dissolved in n,N-dimethylacetamide,
And casting solution is prepared for 8 hours by mechanical agitation at 60 DEG C, the template ion-polymer complex and Kynoar are total
The 15% of casting solution weight is accounted for, casting solution, which stands at least 3 hours, makes bubble discharge completely, is then poured on obtained casting solution clean
On net glass plate, and uniform film is laid into using the scraper for being fixed to 250 μm of gaps at room temperature.Then film is fast
Film solidification is carried out in the deionization water-bath of 25 DEG C of speed immersion, then rinses the film of formation to remove residual solvent；By with containing
The 1mol/L HCl solutions flushing membrane of 1% weight thiocarbamide carries out the elution to template ion, and it is total to obtain Pt (IV) ion blotting
Mixed film.
Further technical solution is：The synthesis route of three thioesters is as follows：By n- dodecyl mereaptan, acetone and first
Base trioctylmethylammonium chloride is mixed into the mixing container, and the NaOH that predetermined amount is slowly added dropwise under cooling and nitrogen protection is molten
Liquid continues to stir the predetermined time, add dissolved with CS2Acetone soln, solution stands the predetermined time after reddening, predetermined amount is added
CHCl3, the NaOH solution of predetermined amount is added, after reacting the predetermined time, the water concentrated hydrochloric acid of predetermined amount is added；Inflation removes more
Remaining acetone filters, and collects solid, and isopropanol is added and filters out insoluble solids, is spin-dried for aqueous isopropanol, obtained solid is multiple
It is recrystallized in normal hexane, obtains three thioesters of yellow solid.
Further technical solution is：The synthesis concrete technology of three thioesters is：By RSH (n- dodecyl mereaptan) (48mL,
40.38g, 0.2mol), acetone (160mL) and methyl tricapryl ammonium chloride (consisting of phase-transferring agent) (3.6mL, 3.2g, 0.008mol) are mixed
In the three-necked flask for closing 1L, it is cooled to 10 DEG C and nitrogen protection.50% NaOH solution is slowly added dropwise, and (16.7g, time is more than
After 20min), continue stir 15min, add dissolved with CS2 (12mL, 15.2g, 0.2mol) acetone (25mL, 20g,
0.3mol) solution, time are more than 20min, and solution reddens after 10min, and CHCl3 (24mL, 35.6g, 0.3mol) is once added, then
50%NaOH solution 80g are added, the time is more than 30min, is reacted one day, and the concentrated hydrochloric acid of 300mL water and 50mL is added.(water and salt
It doesn't matter for the sequencing of acid, does not influence) (first plus hydrochloric acid is more preferable) post-processing：It inflates (4-6h) and removes extra acetone, filter,
Solid is collected, 500mL isopropanols are added and filter out insoluble solids, are spin-dried for aqueous isopropanol, obtained solid is repeatedly in normal hexane
Recrystallization, obtains yellow solid in (80-100mL).(filtrate concentrates recrystallization after collecting) (coloured product will match, different
Continue to recrystallize).
The present invention selects suitable function monomer according to different object ions, using Invertible ideal
(RAFT) method synthesizing amphipathic block copolymer twines wherein with film forming matrix effective macromolecular chain can occur for hydrophobic segment
It ties and then can be effectively anchored in film matrix after film forming, and hydrophilic segment is then because of surface segregation effect enrichment
In film surface, the multifunctional membrane surface with hydrophily and ion identification and binding ability is ultimately formed.
Ion blotting film prepared by the present invention does not need additional cross-linking step, after film curing molding, metal ion
It is directly fixed on membrane material, effective recognition site can be generated after elution.The method is printed relative to traditional ion
Complicated cross-linking process needed for mark material preparation has certain convenience.
It was proved that the present invention prepared by ion blotting film object ion can be shown it is higher affine
Power, not only saturated extent of adsorption is big, but also the rate of adsorption is fast, while having high reusability, and only has after being recycled at five
About 5% initial adsorption capacity loss.
Description of the drawings
The attached drawing for constituting the part of the present invention is used to provide further understanding of the present invention, schematic reality of the invention
Example and its explanation are applied for explaining the present invention, is not constituted improper limitations of the present invention.
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of PMMA and a variety of PMMA-b-P4VP prepared by the present invention；
Fig. 2 is the infrared spectrogram of PMMA and a variety of PMMA-b-P4VP prepared by the present invention；
Fig. 3 is the SEM pictures of a variety of moulds prepared by the present invention；
Fig. 4 is the ATR-FTIR spectrograms of a variety of moulds prepared by the present invention；
Fig. 5 is the static contact angle datagram of the film of a variety of moulds prepared by the present invention；
Fig. 6 is the dynamic contact angle datagram of the film of a variety of moulds prepared by the present invention；
Fig. 7 is the pure water flux datagram of the film of a variety of moulds prepared by the present invention；
Fig. 8, which is the pH of ion blotting blend film prepared by one embodiment of the present invention, influences result figure；
Fig. 9 is ion blotting blend film selective absorption result schematic diagram prepared by one embodiment of the present invention；
Figure 10 is the Dynamic Separation Dependence Results schematic diagram of ion blotting blend film prepared by one embodiment of the present invention；
Figure 11 is that absorption of the ion blotting blend film of one embodiment of the present invention preparation in filtration cycle system is ground
Study carefully result figure；
Figure 12 is the process route chart that one embodiment of the present invention prepares amphipathic block functional polymer.
Specific implementation mode
Present invention will now be described in detail with reference to the accompanying drawings., and the description of this part is only exemplary and explanatory, is not answered
There is any restriction effect to protection scope of the present invention.In addition, description of the those skilled in the art according to this document, it can be right
Feature in this document in embodiment and in different embodiments carries out the corresponding combination.
Experimental raw
Primary raw material is shown in Table 1
Main agents table in the experiment of table 1
Embodiment
Methyl methacrylate removes polymerization inhibitor using the preceding Flash chromatography column through being filled with alkali alumina, and is sealed in
It is kept in dark place at 2 DEG C；Azodiisobutyronitrile is recrystallized three times using preceding in absolute ethyl alcohol, is sealed at 2 DEG C and is kept in dark place；It is poly-
Vinylidene is removed water for 24 hours using preceding be dried in vacuo at 90 DEG C.
The synthesis of three thioesters：By RSH (n- dodecyl mereaptan) (48mL, 40.38g, 0.2mol), acetone (160mL) and methyl
Trioctylmethylammonium chloride (consisting of phase-transferring agent) (3.6mL, 3.2g, 0.008mol) is mixed into the three-necked flask of 1L, is cooled to 10 DEG C simultaneously
Nitrogen protection.After 50% NaOH solution (16.7g, time are more than 20min) is slowly added dropwise, continues to stir 15min, add molten
There is acetone (25mL, 20g, 0.3mol) solution of CS2 (12mL, 15.2g, 0.2mol), the time is more than 20min, and solution reddens
After 10min, CHCl3 (24mL, 35.6g, 0.3mol) being once added, adds 50%NaOH solution 80g, the time is more than 30min,
The concentrated hydrochloric acid of 300mL water and 50mL is added in reaction one day.(it doesn't matter for the sequencing of water and hydrochloric acid, does not influence) (first plus hydrochloric acid
More preferably) post-process：It inflates (4-6h) and removes extra acetone, filter, collect solid, addition 500mL isopropanols filter out insoluble
Solid is spin-dried for aqueous isopropanol, and obtained solid repeatedly recrystallizes in normal hexane (80-100mL), obtains yellow solid.(filter
Liquid concentrates recrystallization after collecting) (coloured product will match, different to continue to recrystallize).
The preparation of 1.Pt (IV) ion blotting blend film
(1) synthesis of Macromolecular chain transfer agent：By 15.0g methyl methacrylates, tri- thioesters reagents of 0.1g and 0.2g are even
Nitrogen bis-isobutyronitrile is dissolved in 36.9mL n,N-Dimethylformamide, and above-mentioned mixed solution is added in reactor, then close
Envelope, after deaerating and being full of nitrogen in the reactor, in 70 DEG C of pre- hot oil bath and holding is continuously stirred reaction and is mixed 6 hours, has reacted
At postcooling to room temperature, the mixture after reaction is diluted with tetrahydrofuran, and precipitated three times in excessive low-temp methanol, most
Afterwards, obtained Macromolecular chain transfer agent is dried in vacuo 24 hours at 40 DEG C；Product is denoted as PMMA-RAFT.
(2) synthesis of amphipathic block functional polymer：The Macromolecular chain transfer agent synthesized in 2.0g steps (1) is taken, with
And 3.0g 4-vinylpridines and 1mg azodiisobutyronitriles are dissolved in 12.3mL dimethylformamides；Above-mentioned mixed solution is added
Enter into reactor, then seal, after deaerating and being full of nitrogen in the reactor, in 70 DEG C of pre- hot oil bath and keeps continuously stirring
Reaction is mixed 6 hours, is cooled to room temperature, the mixture after reaction is diluted with dichloromethane, and excessive low after the completion of reaction
It is precipitated three times in warm methanol；Finally, the amphipathic block functional polymer of acquisition is dried in vacuo 24 hours at 40 DEG C；Product
It is denoted as PMMA-b-P4VP.
(3) synthesis of template ion-polymer complex：Amphipathic block functional polymer 4.00g is taken to be dispersed in 100mL
Containing 50mg templates platinum (IV) ion, pH=0.5 ± 0.1 solution in, then seal and stirring 24 is kept constant at 25 DEG C
Hour, then filtering gained mixture, is washed with deionized and is freeze-dried；
(4) casting film：Template ion-the polymer complex prepared in step (3) and Kynoar dissolving are pressed 3:10
Ratio be dissolved in n,N-dimethylacetamide, and casting solution, the template are prepared for 8 hours by mechanical agitation at 60 DEG C
Ion-polymer complex and Kynoar account for the 15% of casting solution weight altogether, and casting solution, which stands at least 3 hours, keeps bubble complete
Obtained casting solution, is then poured on clean glass plate by full release, and at room temperature using being fixed to scraping for 250 μm of gaps
Knife is laid into uniform film；Then film is immersed rapidly to progress film solidification in 25 DEG C of deionization water-bath, then rinse shape
At film to remove residual solvent.
(5) it elutes：By with the 1mol/L HCl solutions flushing membrane containing 1% weight thiocarbamide wash template ion
It is de-, and obtain Pt (IV) ion blotting blend film.It is denoted as Pt (IV)-IIM.
2. the preparation of non-trace blend film
The preparation method of non-trace blend film is same as above, in addition to being added without template ion.
3. the structure and performance characterization of amphipathic block functional polymer PMMA-b-P4VP
(1) nuclear magnetic resonance spectroscopy (1H NMR)
The hydrogen nuclear magnetic resonance spectrogram of PMMA and three kinds of amphipathic block functional polymer PMMA-b-P4VP are in such as Fig. 1 institutes
Show, wherein PP1, PP2 and PP3 are respectively amphipathic block functional polymer (the block length PP1 of three kinds of B block length<
PP2<PP3).Chemical shift at 3.60ppm can belong to methoxyl group-CO-CH3(MMA is at the peak of a).In addition,
Chemical shift at 1.25ppm is related with the hydroxyl of RAFT terminals.Such as three kinds of PMMA-b-P4VP copolymers1Shown in HNMR spectrums,
Most significant variation is that all occur new chemical shift at 8.33ppm and 6.38ppm in the spectrum, they all belong to pyridine ring
CH groups (4VP is at the peak of c-d).Other chemical shifts also exist1It is marked in HNMR spectrums.It can be seen from the figure that 8.33ppm
With the chemical shift area of 6.38ppm as the increase of polymerization time (increasing to 10h from 2h) is also increasing.These the result shows that
PMMA-b-P4VP copolymers composition having the same, and in different PMMA-b-P4VP amphipathic nature block polymers, parent
Water chain P4VP length is different.
(2) infrared spectrum (FTIR)
The infrared spectrum of PMMA and three kinds of amphipathic block functional polymer PMMA-b-P4VP are as shown in Fig. 2, main inhale
Peak is received to be marked in figure.In 1730cm-1Peak belong to the stretching vibration of carbonyl (there are C=O groups in PMMA segments).With
PMMA spectrograms are compared, and after RAFT polymerizations occur for 4VP and PMMA, apparent variation has occurred in polymer architecture.As shown,
In 1599cm-1And 1556cm-1Place there are two new absorption band, correspond to respectively C=N in P4VP segments on fragrant pyridine ring with
C-C stretching vibrations.This demonstrate that after 4VP and PMMA carry out RAFT polymerizations, block functional polymer PMMA-b-P4VP at
Work(synthesizes.With the increase in reaction time, B block peak intensity increases with A block peak intensity ratios.This, which is also indicated that, has synthesized difference
The PMMA-b-P4VP block functional polymers of B block length.
1It is required product that the result of H NMR and FTIR, which demonstrate synthesized amphiphile function polymer,.In addition, because
PMMA has entanglement effect with PVDF molecule interchains, so when this amphiphile function polymer possesses the higher hydrophobicity of molecular weight
When PMMA segments, it can not only ensure that amphiphile function polymer is securely anchored on film matrix PVDF, while can also be really
Protect the loss for reducing hydrophily P4VP segments in film-forming process to the greatest extent.
(3) gel permeation chromatography (GPC)
The gpc analysis data of PMMA, PP1, PP2 and PP3 are as shown in table 2, and number-average molecular weight (Mn) is listed in table 2,
Weight average molecular weight (Mw), Z-average molecular weight (Mz), the dispersion degree of peak molecular weight (Mp) and copolymer.It can be with from GPC test results
It obtains, PP1, the number-average molecular weight of PP2 and PP3 are respectively 7.05 × 104, 7.57 × 104With 7.86 × 104g/mol.PMMA's
Number-average molecular weight is 6.45 × 104.It can be seen that the molecular weight of diblock copolymer is much larger than the molecular weight of PMMA.These results
Show to be successfully prepared the PMMA-b-P4VP block functional polymers with different B block molecular weight.In short, successfully synthesizing
Amphipathic block functional polymer PMMA-b-P4VP.
Table 2GPC analyzes data
aDetection from GPC
The structure and performance characterization of 3.Pt (IV) ion blotting blend film
For casting solution by PVDF, additive and different kinds of liquid solvents composition, additive is PP1~PP3 described above, molten
The mixing composition of agent such as DMAc, DMF or DMF and THF are listed in table 3.
3 casting solution of table forms
(1) scanning electron microscope (SEM)
The present invention is prepared for eight kinds of films of M0~M7 altogether, uses the surface of sem analysis PVDF/PMMA-b-P4VP films and transversal
The form in face is simultaneously shown in Figure 3.It can be seen from the figure that PVDF/PMMA-b-P4VP films (M1 to M7) have and pure pvdf membrane
(M0) basically same structure feature.It is made of a fine and close surface and the porous bottom layer with finger.However,
PVDF/PMMA-b-P4VP films (M1 to M7) illustrate the finger-like porous structure than pure pvdf membrane (M0) bigger.In PVDF/PMMA-
It is due to the amphipathic copolymer in casting solution that larger finger is formed on the porous bottom layer of b-P4VP films (M1 to M7)
The presence of the P4VP segments of PMMA-b-P4VP causes the moment of Casting solution to be layered, to form larger finger.So
And M1, M2 and M3 are analyzed it can be found that film thickness follows M1<M2<The trend of M3, in this case, it may be possible to because
Amphipathic copolymer p P3 containing longest P4VP chains in M3 Casting solutions, when Casting solution is immersed in water coagulating bath, PP3
Can be most fast shift to film surface (be PP2 faster, slow be PP1), then can quickly form film surface layer.With further solvent
It flows out from casting solution and is prevented by cortex, film shrinking percentage is minimum.Therefore, the M3 that thickness is about 125 μm is most thick in three.With M3
It compares, there is smaller thickness using DMF as the M4 prepared by solvent.This may be due to DMAc compared with DMF to PVDF
With stronger solvent power.In other words, compared with DMF, the mutual affinity between PVDF and DMAc is stronger, leads to membrane system
Some entanglement of solvent in system.But this is not confirmed.In addition, the M5 of about 29.47 μm of thickness is all films (M0 to M7)
In it is most thin.This phenomenon may be netted due to forming porous (aperture is from 200 to 300nm) in film formation initial stage film surface
The result of structure.Solvent flows out during inversion of phases, film shrinking percentage highest.Another possible reason may be mixed solvent
Middle THF evaporations are more, cause film made of inversion of phases relatively thin.Therefore, M5 is most thin.Yang et al. also observes similar show
As.In addition, it is observed that the presence of spongy sublayer between cortex and the big gap of finger-like.This can be by THF in solvent
Local evaporation in mixture is explained.Polymer concentration increases in film surface, leads to the big gap of slower layering and delay
It is formed.According to the analysis of M3 and M6, when a small amount of copolymer is added, it can be found that film thickness M6<M3.This result can use heating power
The factor is learned to explain.Moment liquid-liquid can be caused to be layered when a small amount of copolymer is as additive in Casting solution, the total thickness of film
Degree increases with the increase of copolymer concentration.However, further increasing for copolymer concentration may delay kinetics
And generate relatively thin film.Therefore, film thickness M7<M3.
(2) porosity of film
The present invention is prepared for eight kinds of films of M0~M7 altogether, and the porosity of different films is as shown in table 4, and the porosity of M1-M3 is gradually
Increase, this can be confirmed from sem analysis before.With the increase of polymerization time, hydrophilic chain P4VP is lengthened, and forms a film it
Afterwards increase the size of section fenestra, to which pore volume increases, porosity increases.For M6, M3, M7, with functional polymer
40% is increased to from 20% with the ratio of PVDF, the porosity of film is also increasing, this is the knot that hydrophilic chain P4VP pores effect is reinforced
Fruit.Further, since the size in the cortex hole of M5 is much greater compared to the size in other hymeniderm layer holes, and got over according to membrane volume
Small, the bigger principle of porosity, its porosity of comprehensive analysis is also larger.
4 analysis of porosity data of table
The porosity of a membrane matrixs impregnates the method for determination by ethyl alcohol.
B determines film thickness according to SEM image
(3) the ATR-FTIR spectrum of film
The decaying In situ ATR-FTIR of M0~M7 as shown in figure 4, film M0 in wave number 1181cm-1And 1072cm-1It is right respectively
Answer-CF2With the stretching vibration peak of C-F, 900-800cm-1In the range of vibration peak belong to the crystallization vibration peak of PVDF；According to
Above to the analysis result of amphipathic block functional polymer PMMA-b-P4VP, corresponding stretching vibration peak 1730cm-1、
1599cm-1、1556cm-1It is respectively belonging to C=N and C-C stretching vibrations present in carbonyl C=O, fragrant pyridine ring；For
Shown in PMMA-b-P4VP/PVDF films such as Fig. 4 (M1-M7), occur being respectively belonging on this spectral line PMMA-b-P4VP and
The feature stretching vibration peak of PVDF.In addition, 1730cm after film forming-1The peak at place is moved to 1728cm-1, this be PMMA segments with
The result that PVDF has an effect.Above analysis shows being had occurred between amphiphile function polymer P MMA-b-P4VP and PVDF good
Compatible behavior, as needed for.
(4) film surface contact angle
Fig. 5 and Fig. 6 illustrates the static contact angle and dynamic contact angle of film, as shown, the static contact angle of pvdf membrane
It is 74.5 °, reflects its strong hydrophobicity.By being blended with PMMA-b-P4VP, prepared PMMA-b-P4VP/PVDF is blended
The contact angle of film is declined, while meaning that their hydrophily is reinforced；These analytical proofs are in NIPS
In film-forming process, hydrophilic segment can effectively move to the surface of film, therefore the hydrophily of trace blend film can lead to
Cross being strengthened for these hydrophilic radicals that effectively enrichment is got up.For M6, M3, M7, when Amphipathilic block polymer with
The ratio of PVDF from 20% increase to 40% when, contact angle occur reduce trend.Explanation for this phenomenon is：
During NIPS, hydrophilic segment P4VP in Amphipathilic block polymer can move to the surface of film because surface segregation acts on
On, so that the hydrophily of film surface is strengthened.In addition, the contact angle that M5 starts is very much because film surface is very coarse greatly,
And M3 illustrates the dynamic contact angle of rapid decay in dynamic contact angle, therefore illustrate that its fenestra has stronger hydrophily.
M0 films still show very strong hydrophobicity, therefore larger decaying does not occur within the testing time for its dynamic contact angle.With M0
It compares, M1 shows the hydrophily of reinforcement.During NIPS, hydrophilic segment can move to upper surface and the fenestra of film
Surface, these enrichment P4VP segments increase along with the increase of amphipathic copolymer content, so as to cause the hydrophily of film
Further reinforced.On the other hand, the presence of macroporous structure also results in dynamic contact angle and drastically reduces in a short time.
(4) pure water flux
Influence of the above-mentioned different films to pure water flux is enumerated in Fig. 7.Pure pvdf membrane (M0) due to its strong hydrophobicity,
Therefore effective pure water flux is not detected under the operating pressure of 0.1MPa.For M1-M3, due to amphipathic block polymerization
The introducing of object, their pure water flux have obtained apparent rising, in addition, when functional polymer generated time increases, PMMA-
The pure water flux of b-P4VP/PVDF blend films increases to 80.44L m from 61.77-2h-1.This is because the lengthening of hydrophilic chain P4VP makes
The size of section fenestra increases, i.e., membrane pore size increases and strengthen passing through for pure water, therefore has larger pure water flux.When
When solvent is DMF+THF, the pure water flux of PMMA-b-P4VP/PVDF blend films is much greater compared to the blend film of other solvents,
This is because the cortex pore size of film is larger, therefore water resistance reduces, and pure water flux increases.
The performance study of 4.Pt (IV) ion blotting blend film
(1) influence of PH
As shown in figure 8, at ranging from 0.5 to 3 pH, trace blend film shows Pt (IV) ion higher affine
Power, but as the pH value of solution increases to 3 to 4.5, adsorption capacity reduces rapidly.These results may be attributed to following original
Cause：At lower ph, on the one hand, metal ion platinum is in acid condition with [PtCl6]2-Form exists；On the other hand, work(
The ligand groups of energy property polymer can protonate in an acidic solution, then pass through electrostatic interaction [PtCl6]2-It is inhaled
It guides on functional polymer and has an effect.When pH is 3 to 4.5, since the ligand groups of functional polymer protonate
Declines, so functional polymer and [PtCl6]2-Between electrostatic interaction reduce, to adsorption capacity decline.Separately
Outside, when pH value is higher than 4.5, since platinum ion is with Pt (OH)4The form of precipitation exists, so further absorption test is difficult to
It executes.Therefore, in order to make acquisition IIM have maximal absorptive capacity to Pt (IV), the pH value of solution should adjust to 0.5.
(2) selective absorption
In order to assess the Selective Separation characteristic of Pt (IV)-IIM, contain Pt (IV), Cu (II) and Ni (II) at the same time
The competitive Adsorption of different kinds of ions is studied in ternary mixed solution.Pt (IV)-IIM and NIM are respectively to Pt (IV), Cu (II) and Ni
(II) uptake is as shown in Figure 9.It can be seen that Pt (IV)-IIM have high selectivity to Pt (IV), and it is 0.5 in pH
When ± 0.1 in solution, the presence of Cu (II) and Ni (II) ion have no significant effect the adsorbance of Pt (IV), this shows Pt
(IV)-IIM can keep good adsorptive selectivity in the case of competing ions to platinum ion.This is because printing process produces
Raw trace effect makes Pt (IV)-IIM have specific recognition ability to platinum ion.Pt (IV)-IIM preferentially identifies Pt (IV), this card
Being successfully formed for imprinted cavity is illustrated has excellent shape memory effect with Pt (IV)-IIM.The K of Pt (IV)dValue is significantly greater than
The K of other metal ionsdValue.Therefore, selectivity systems of Pt (the IV)-IIM for Pt (IV)/Cu (II) and Pt (IV)/Ni (II)
Number is respectively 13.689 and 23.228.It is obvious that in the acidic aqueous solution that three metal ion species coexist, Pt (IV)-IIM is to Pt
(IV) with very strong selective absorption.
(3) Pt (IV) is detached during membrane filtration
Using 5mg/L Pt (IV) aqueous solutions as charging original solution, the effective filtration area of film is 38.5cm2, it is in pH
The filtration experiment of 0.5 ± 0.1 time progress Pt (IV)-IIM, breakthrough curve are as shown in Figure 10.Due on the surface and hole of originally film
There are many ion-binding sites on wall, therefore Pt (IV) ions fed in original solution were effectively adsorbed at first 40 minutes.With
It is effectively combined site to be occupied, part Pt (IV) ion in feedstock solution cannot be adsorbed and start to leak.When effective
Binding site is occupied completely, and it is to feed the concentration of original solution that percolating solution concentration, which reaches maximum value,.Therefore, area is
38.5cm2Film can handle 120mL charging original solutions until break through (40 minutes).In addition, P4VP chains in this research
Content is relatively low.It can also be held in practical applications to improve Pt (IV) absorption by introducing more P4VP chains into film
Amount.
(4) it regenerates
In order to study the reusability of Pt (IV)-IIM, five are repeated with the same Pt (IV)-IIM at optimum conditions
Secondary absorption-elution cycles.Make Pt (IV)-IIM of adsorption saturation again with the 1mol/L HCl solutions containing 1wt% thiocarbamides
It is raw.The maximum adsorption capacity recycled every time is as shown in figure 11, it is known that, Pt (IV)-IIM still keeps high-caliber after 5 cycles
Adsorbance.Initial adsorption capacity only loses about 5.1%, shows that Pt (IV)-IIM is chemically stable, and ensuring effective platinum
It can be recycled for multiple times under absorbing.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of ion blotting blend film, which is characterized in that include the following steps：
(1) synthesis of Macromolecular chain transfer agent：By methyl methacrylate, RAFT reagents and thermal initiator in scheduled ratio
It is added in reactor, seals after addition solvent and reacted under a shielding gas, precipitation filtering is carried out after the completion of reaction, will
To solid product be dried to constant weight；
(2) synthesis of amphipathic block functional polymer：By what is synthesized in 4-vinylpridine, thermal initiator and step (1)
Macromolecular chain transfer agent is added in scheduled ratio to reactor, seals and is reacted after addition solvent, reaction is completed laggard
Row precipitation filtering, obtained solid product is dried to constant weight；
(3) synthesis of template ion-polymer complex：The amphipathic block functional polymer dispersion that will be synthesized in step (2)
In the container equipped with template ion aqueous solution, then sealing reaction is filtered after reacting fully, is washed with deionized simultaneously
Freeze-drying；
(4) casting film：By in step (3) template ion-polymer complex and film matrix be dissolved in solvent in scheduled ratio
The middle stirring predetermined time obtains casting solution to uniformly mixed, casting solution is stood predetermined time removing bubble, then by casting solution
Film-forming plates are poured into, and casting solution is laid into uniform film, in the deionized water that the film is immersed rapidly to predetermined temperature
Film solidification is carried out in bath, washing film removes residual solvent；
(5) it elutes：Using the membrane elution template ion prepared in eluant, eluent rinsing step (4), obtains the ion blotting and be blended
Film.
2. the preparation method of ion blotting blend film according to claim 1, which is characterized in that the step (1) and step
Suddenly in (2), the RAFT reagents, thermal initiator and solvent are respectively three thioesters, azodiisobutyronitrile and N, N- dimethyl formyls
Amine.
3. the preparation method of ion blotting blend film according to claim 2, which is characterized in that in the step (4)
Film matrix and solvent are respectively Kynoar and DMAC N,N' dimethyl acetamide.
4. the preparation method of ion blotting blend film according to claim 3, which is characterized in that in the step (5)
Eluant, eluent is the mixed solution of thiocarbamide and hydrochloric acid.
5. the preparation method of the ion blotting blend film according to any one of claim 2~4, which is characterized in that institute
It states methyl methacrylate and removes polymerization inhibitor using the preceding Flash chromatography column through being filled with alkali alumina, and be sealed at 2 DEG C
It is kept in dark place；The azodiisobutyronitrile is recrystallized three times using preceding in absolute ethyl alcohol, is sealed at 2 DEG C and is kept in dark place；Institute
Kynoar is stated to remove water for 24 hours using preceding be dried in vacuo at 90 DEG C.
6. the preparation method of ion blotting blend film according to claim 5, which is characterized in that in the step (1)
Concrete technology is：By 15.0g methyl methacrylates, tri- thioesters reagents of 0.1g and 0.2g azodiisobutyronitriles are dissolved in 36.9mL
In n,N-Dimethylformamide, above-mentioned mixed solution is added in reactor, is then sealed, deaerate and is full of in the reactor
After nitrogen, in 70 DEG C of pre- hot oil bath and holding is continuously stirred reaction and is mixed 6 hours, is cooled to room temperature after the completion of reaction, after reaction
Mixture diluted with tetrahydrofuran, and precipitate three times in excessive low-temp methanol, finally, obtained macromolecular chain shifted
Agent is dried in vacuo 24 hours at 40 DEG C.
7. the preparation method of ion blotting blend film according to claim 6, which is characterized in that in the step (2)
Concrete technology is：Take the Macromolecular chain transfer agent synthesized in 2.0g steps (1) and 3.0g 4-vinylpridines and 1mg azos
Bis-isobutyronitrile is dissolved in 12.3mL dimethylformamides；Above-mentioned mixed solution is added in reactor, is then sealed, degassing is simultaneously
After being full of nitrogen in the reactor, in 70 DEG C of pre- hot oil bath and holding is continuously stirred reaction and is mixed 6 hours, is cooled to after the completion of reaction
Room temperature dilutes the mixture after reaction with dichloromethane, and is precipitated three times in excessive low-temp methanol；Finally, it will obtain
Amphipathic block functional polymer be dried in vacuo 24 hours at 40 DEG C.
8. the preparation method of ion blotting blend film according to claim 7, which is characterized in that in the step (3)
Concrete technology is：It takes amphipathic block functional polymer 4.00g to be dispersed in 100mL and contains 50mg templates platinum (IV) ion, pH=
It in 0.5 ± 0.1 solution, then seals and keeps constant stirring 24 hours at 25 DEG C, then filtering gained mixture, spends
Ion water washing is simultaneously freeze-dried.
9. the preparation method of ion blotting blend film according to claim 8, which is characterized in that the step (4) and step
Suddenly the concrete technology in (5) is：Template ion-the polymer complex prepared in step (3) and Kynoar dissolving are pressed
3:10 ratio is dissolved in n,N-dimethylacetamide, and prepares casting solution within 8 hours by mechanical agitation at 60 DEG C, described
Template ion-polymer complex and Kynoar account for the 15% of casting solution weight altogether, and casting solution, which stands at least 3 hours, makes gas
Full release is finished, is then poured on obtained casting solution on clean glass plate, and at room temperature using being fixed to 250 μm of gaps
Scraper be laid into uniform film；Then film is immersed rapidly to progress film solidification in 25 DEG C of deionization water-bath, then rushed
The film to be formed is washed to remove residual solvent；By being carried out to mould with the 1mol/L HCl solutions flushing membrane containing 1% weight thiocarbamide
The elution of plate ion, and obtain Pt (IV) ion blotting blend film.
10. the preparation method of ion blotting blend film according to claim 6, which is characterized in that the conjunction of three thioesters
It is as follows at process route：By n- dodecyl mereaptan, acetone and methyl tricapryl ammonium chloride are mixed into the mixing container, cooling
And the NaOH solution of predetermined amount is slowly added dropwise under nitrogen protection, continue to stir the predetermined time, add dissolved with CS2Acetone it is molten
Liquid, solution stand the predetermined time after reddening, and the CHCl of predetermined amount is added3, the NaOH solution of predetermined amount is added, pre- timing is reacted
Between after, the water concentrated hydrochloric acid of predetermined amount is added；Inflation removes extra acetone, filters, and collects solid, and isopropanol is added and filters out not
Molten solid, is spin-dried for aqueous isopropanol, and obtained solid repeatedly recrystallizes in normal hexane, obtains three thioesters of yellow solid.
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| CN110538584A (en) * | 2019-07-26 | 2019-12-06 | 湖南科技大学 | Preparation method of palladium ion imprinted copolymer membrane and application of palladium ion imprinted copolymer membrane |
| CN112358643A (en) * | 2020-11-10 | 2021-02-12 | 浙江工业大学 | Preparation method of homogeneous pore membrane based on block copolymer bulk polymerization |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110538584A (en) * | 2019-07-26 | 2019-12-06 | 湖南科技大学 | Preparation method of palladium ion imprinted copolymer membrane and application of palladium ion imprinted copolymer membrane |
| CN110538584B (en) * | 2019-07-26 | 2021-07-20 | 湖南科技大学 | Preparation method of palladium ion imprinted copolymer membrane and application of palladium ion imprinted copolymer membrane |
| CN112358643A (en) * | 2020-11-10 | 2021-02-12 | 浙江工业大学 | Preparation method of homogeneous pore membrane based on block copolymer bulk polymerization |
| CN112358643B (en) * | 2020-11-10 | 2022-09-30 | 浙江工业大学 | Preparation method of homogeneous pore membrane based on block copolymer bulk polymerization |
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