CN102702564A - Preparation method of charging polyvinylidene fluoride blend porous membrane with ion sensitivity and product - Google Patents
Preparation method of charging polyvinylidene fluoride blend porous membrane with ion sensitivity and product Download PDFInfo
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Abstract
The invention discloses a preparation method of a charging polyvinylidene fluoride blend porous membrane with ion sensitivity. Methyl methacrylate (MMA) and polymerizable imidazole ionic liquid halogenated salt (IL) containing double bonds are used as a reaction unit; a charging block polyion liquid brush copolymer (PMMA-b-PIL) is synthetized by reversible addition-fragmentation chain transfer (RAFT), and then the copolymer is used for blending modification of a polyvinylidene fluoride (PVDF) membrane. The membrane prepared by the preparation method disclosed by the invention has remarkable ion sensitive characteristics. Both the molecular weight and the distribution of the polyion liquid brush block copolymer prepared by the preparation method are easily controlled. The reaction condition is easier to achieve. The preparation method is easy to industrialize, and has excellent application prospects in the aspects such as water treatment, controlled release, a chemical sensor, a fuel cell and the like.
Description
Technical field
The invention belongs to the membrane technique field, particularly a kind of preparation method with poly ion liquid brush charged porous polyvinylidene blending porous membrane block copolymer-modified, that have ion-sensitive.
Background technology
Membrane technique is a kind of fluid separation techniques efficiently; Compare with traditional stripping technique (like distillation etc.) have the efficient height, characteristics such as energy consumption is low, easy and simple to handle, environmentally safe, in energy-saving and cost-reducing, cleaner production and recycling economy, bringing into play more and more important effect.In membrane sepn, mould material plays keying action, and people are developed to direction functional, the environmental sensitivity mould material from the traditional commodities mould material the research of macromolecule member material gradually at present.Different with the traditional commodities separatory membrane; Containing in the environment sensitive film stimulates group or the segment of making reversible reaction to external world; Thereby make the structure of film change and change reversiblely with external stimulus; Cause the change of film properties such as pore size, parent/hydrophobicity etc., thus the flux of controlling diaphragm, the selectivity of raising film.At present, mould material surface-functionalized become a new direction of current parting material field development, is considered to being 21 century membrane science and one of the important development direction of technical field.Functional membrane has important potential using value in many fields such as sustained release, chemical separation, fuel cell, chemical sensor, artificial organ, water treatments.
Aspect the preparation of environmental sensitivity film; Cause that at first parent/hydrophobic reversible conversion film that people pay close attention to is the temperature sensitivity film; Its action principle is when the residing envrionment temperature of polymeric film changes, and sharp response and the variation of hop property take place thereupon for the pore size of film, parent/hydrophobicity etc.Gather (N-NSC 11448) and (PNIPAM) have a very strong temperature sensitive polymer; Its polymer chain (is about 32 ° of C) and becomes micelle shape structure (Globule) closely by loose ball of string structure (Coil) near lower critical solution temperature LCST; Promptly taken place to roll up transformation, thereby produced temperature sensitive property from being stretched over.Has the temperature sensitive characteristic according to PNIPAM; Someone grafts on poly N-isopropyl acrylamide PNIPA and has prepared the temperature responsive intelligent film on the product film; And use it for the hydrophilic, hydrophobic fractionation by adsorption experiment of film, find that this mould material has fine surperficial automatically cleaning characteristic.In addition, people have prepared pH response film, molecular recognition response film, electric field response film, pressure response membrane, photoresponse film etc. according to some polymer segment respectively to the response characteristic of pH, light, electric field and pressure etc.
See from the preparation method; Environmental sensitivity mould material commonly used at present mainly is to prepare through the surface grafting method; The surface grafting method is to pass through chemistry (radical initiator, ozone etc.) or physical means (like UV-light, plasma body, high-energy irradiation etc.) earlier in formation reaction active site, existing commercial polymer film surface; Utilize these active site to cause other monomers then, thereby generate " polymer brush " at the film surface aggregate.This environment-responsive polymer brush mainly contains: what have temperature sensitivity mainly contains poly N-isopropyl acrylamide etc., has mainly containing ROHM, polymethyl acrylic acid and gathering ethylacrylic acid etc. of pH responsiveness.Though the grafting method is the strong instrument of preparation environment sensitive functional membrane; But the grafting method also exists the shortcoming that self is difficult to overcome; Be that film surface aggregate thing segmental molecular weight and the polymer segment grafting density on the film surface is difficult to control; Cause the membrane surface structure irregularity, thereby influenced the separation of film.
In numerous method of modifying, blending and modifying since film forming and modification carry out synchronously, have simple to operate, affinity is easy to adjust, can realize the advantages such as mutual supplement with each other's advantages between differing materials, becomes generally acknowledged, that have development potentiality at present porous-film modification technology.But the component of polymer that blending and modifying requires to participate in blend has certain consistency to each other, so the successful key of blending and modifying is to develop the amphiphilic macromolecular properties-correcting agent of excellent performance.
In the European patent EP 1339777; Earlier on the PVDF chain, introduce polymethyl acrylic acid (PMMA) segment through ATRP; Prepared a kind of amphipathic large molecule surface modifier, and itself and PVDF blend have been prepared a kind of PVDF blended porous membrane of the pH of having responsiveness.In addition; To adopting amphiphilic macromolecular that PVDF is carried out blending and modifying; Also carried out a large amount of research both at home and abroad; Synthesized numerous amphiphilic macromolecular properties-correcting agent such as PVDF-g-POEM, P (MMA-r-POEM), PVDF-g-P (PEGMA), PVDF-g-PMAGlc, and will also obtain very big success aspect the hydrophilic modification of pvdf membrane, these research explanations are used for amphipathic multipolymer the possibility of film modification.Chinese invention patent application CN1743351 (open day is on March 8th, 2006) discloses a kind of preparation method of temperature-sensitive polyvinylidene fluoride intelligent membrane material; This method is to be grafted monomer with N-NSC 11448 (NIPA), and PVDF is a macromole evocating agent, is catalyzer with the cuprous chloride; 4; 4 '-dimethyl--2, the 2-dipyridyl is a ligand, adopts the method preparation of atom transferred free radical to have the material modified PVDF-g-PNIPA of temperature-sensitive polyvinylidene fluoride intelligent membrane; This properties-correcting agent can be used for the study on the modification of pvdf membrane, has the separation membrane material of temperature sensitive property with preparation.
In sum; Prepared environmental sensitivity film mainly is to launch research to pH value susceptibility and temperature sensitivity film at present; The polymerization single polymerization monomer of being selected for use mainly is grafted monomer such as vinylformic acid, methylacrylic acid and the different acrylic amide of N-, and Shang Weijian is used for polymerizable type ionic liquid the synthetic preparation of segmented copolymer.Prepared method mainly comprises surface graft modification and two kinds of means of blending and modifying of film.Membrane surface modification mainly exists film surface aggregate thing segmental molecular weight and the grafting density of polymer segment on the film surface to be difficult to control, causes film top layer pore structure to diminish.Problems such as obstruction, thus the separation of film influenced.In the blending and modifying; The main ATRP (ATRP) that adopts prepares graft copolymer; In the preparation process, there is reaction conditions harsh polymerizing conditions such as (anhydrous) anaerobics like needs; And also exist grafting density, percentage of grafting and the molecular structure of graftomer and molecular weight to be difficult to difficult problems such as control, and problems such as color change also can take place in synthetic PVDF graft copolymer, influence its application in film modification preparation greatly.
In recent years, ionic liquid receives much concern as one type of efficient green solvent, and the designability of ionic liquid structure, highly charged property and ion-sensitive characteristic etc. also become the emphasis that people pay close attention to.(Vijayakrishna K. such as Vijayakrishna; Jewrajka S.K.; Ruiz A.; Et al. " Synthesis by RAFT and Ionic Responsiveness of Double Hydrophilic Block Copolymers Based on Ionic Liquid Monomer Units. " Macromolecules; 41 (2008), 6299-6308) find that the multipolymer that contains the ionic liquid block has good ion-sensitive characteristic, and think that the factor that causes ion-sensitive is because of hydrophilic Br in the multipolymer
-Can with salts solution in-N (SO
2CF
3)
2 -Deng negatively charged ion generation exchange interaction, thus cause the ionic liquid multipolymer by hydrophilic to hydrophobic conversion.In addition, also have a lot of scientists also to attempt polymerizable type ionic liquid is grafted to single crystalline Si or gold thin film surface through chemical reaction, and through with its with to anionic permutoid reaction to find film surface parent/hydrophobicity conversion of energy.People mainly are used for the ionic liquid segmented copolymer reversible regulation and control of compact inorganic thin-film material surface wellability and conductivity research aspects such as silicon single crystal, gold at present; And its method of modifying mainly adopts surface grafting polymerization thing technology, and Shang Weijian is used for porous diffusion barrier Study on Surface Modification report with the ionic liquid segmented copolymer.
Our inventor thinks the important structure unit of poly ion liquid brush segmented copolymer as a kind of green, charged, the reversible adjusting of wettability; Significant to improving the mould material surface property, the preparation that the characteristics of utilizing poly ion liquid to brush segmented copolymer can be the ion-sensitive blended porous membrane provides a kind of universality novel method.
Summary of the invention
Preparing method's goal of the invention of the present invention is to provide a kind of preparation method with charged porous polyvinylidene blending porous membrane of ion-sensitive, and prepared blend film all has good application prospects at aspects such as water treatment, sustained release, fuel cell, chemical sensors.
Preparing method of the present invention adopts following technical scheme:
A kind of preparation method with charged porous polyvinylidene blending porous membrane of ion-sensitive is characterized in that comprising the steps:
(1) polymethylmethacrylate RAFT macromolecular chain transfer agent is synthetic: with MMA MONOMER, small molecules RAFT chain-transfer agent and initiator Diisopropyl azodicarboxylate (AIBN); Mol ratio according to 100:1:0.33 adds in the reactor drum; And adding solvent 1; The 4-dioxane is in high-purity N
2Mixing and stirring under the gas shiled, logical N
2After the 40min; With reaction flask sealing and move in the 60-70 ℃ of oil bath reaction after 12-20 hour, reaction flask is immersed rapidly carry out quenching in ice/water mixture with termination reaction, then; With methyl alcohol polymer precipitation is come out; And clean 2-5 time repeatedly with methyl alcohol, throw out to constant weight, obtains faint yellow polymethylmethacrylate macromolecular chain transfer agent (PMMA-R) in 40 ℃ of following vacuum-dryings;
(2) charged block poly ion liquid brush multipolymer is synthetic: PMMA-R macromolecular chain transfer agent, polymerizable type imidazolium halide ionic liquid (IL) and AIBN that step (1) is obtained are dissolved in the solvent DMF of nitrogen atmosphere; PMMA-R wherein: polymerizable type imidazolium halide ionic liquid (IL) mol ratio is 1:20 ~ 1:80; AIBN is 0.1% of a gross weight; Behind the logical nitrogen 40min with the reaction flask sealing and move in 60-70 ℃ of oil bath and react 12-24h; Back quenching and deposition, throw out obtain charged block poly ion liquid brush multipolymer more than 40 ℃ of following vacuum-drying 48h;
(3) preparation of charged porous polyvinylidene blending porous membrane: charged block poly ion liquid is brushed multipolymer, pvdf, pore former and solvent according to being configured to film-casting liquid; At 60-70 ℃ of following stirring reaction 12-24 hour; Discontinuous degassing then; And on dull and stereotyped carrier with the nascent dull and stereotyped liquid film of scraper striking 150-250 μ m, and be 20-40 ℃ in temperature, relative humidity is to stop below 40 seconds in the air of 40-80%; With film-forming in the water-bath of 20-40 ℃ of the nascent liquid film immersion on the dull and stereotyped carrier, the composition of described film-casting liquid and mass percent are: pvdf: molecular weight is 1 * 10
5~ 2 * 10
6, 10-12%; Charged block poly ion liquid brush multipolymer: 1-8%; Pore former: molecular weight is the polyoxyethylene glycol of 200-20000,2-4%; Solvent: N, dinethylformamide, DMAC N,N or N-Methyl pyrrolidone, 82%.
Described RAFT chain-transfer agent is a dithio RAFT reagent, is preferably a kind of in S-1-dodecyl-S '-(α, α '-dimethyl--α " vinylformic acid) dithiocarbonates or dithiobenzoic acid isopropyl cyanide ester or the dithio naphthoate.
Below be their molecular structural formula:
Further, said polymerizable type imidazolium halide ionic liquid (IL) mainly is meant allyl group (or acryloxy) the ionic liquid halide salt that contains different carbon chain lengths, described halogen ion X
-Be meant Br
-(or Cl
-) ion, the molecular structural formula of polymerizable type imidazole ion liquid is:
Halogenated alkenes propyl group ionic liquid halogenation acryloxy ionic liquid.
Said preparation method comprises that also the gained blended porous membrane carries out parent/hydrophobic conversion through film to anionresin; Carry out ion exchange reaction 0.5-6 hour in the salt brine solution with prepared blend film immersion different concns negatively charged ion composition, to realize hydrophilic Br in the poly ion liquid brush
-(or Cl
-) ion and hydrophobic to the exchange between the negatively charged ion, selectedly commutative ion is preferably [BF
4]
-, [PF
6]
-,-C (CF
3SO
2)
3 -,-C (C
2F
3SO
2)
3 -Deng, the concentration of salt brine solution is 0.5-50mM.
Charged block poly ion liquid brush multipolymer described in the step (2) is meant that mainly with polymethylmethacrylate (PMMA) be hydrophobic segment, is the multipolymer of hydrophilic block with poly ion liquid brush (PIL), is PMMA-b-PIL.
Has a charged porous polyvinylidene blending porous membrane of ion-sensitive by the bright preparing method's system of this law; The aperture of film is 0.01 ~ 5.0 micron; Thickness is the 50-250 micron, and porosity is the flat sheet membrane of 45-80%, and the film initial contact angle is less than 80 °; Film has ion-sensitive, reaches more than 100 ° with the contact angle of anionresin caudacoria in the salts solution.
Compare prior art, preparation method of the present invention has following beneficial effect:
(1) preparation method of the present invention with TEB 3K (MMA) and the polymerizable type imidazole ion liquid halide salt (IL) that contains two keys as reaction member; Through the synthetic charged block poly ion liquid brush of reversible addition-fracture chain transfer polymerization (RAFT) multipolymer (PMMA-b-PIL), then this multipolymer is used for the blending and modifying of pvdf (PVDF) film.Because PMMA block and pvdf in this segmented copolymer have good consistency; Poly ion liquid brush block (PIL) has good charge and wetting ability; Therefore both can realize the consistency of itself and PVDF at this multipolymer of modifying process; Can obviously improve the charge and the wetting ability on pvdf membrane surface again, and through the reversible transition of anionic exchange in this film and the salts solution with realization film surface wettability.
(2) the present invention brushes segmented copolymer through the synthetic poly ion liquid of " activity "/controllable free-radical polymerisation technology (RAFT), the molecular weight of multipolymer and controllable molecular weight distribution, and synthesis technique is simple relatively, is prone to realize extensive synthetic.The blend method preparation is adopted in the preparation of the charged porous polyvinylidene blending porous membrane of ion-sensitive, thereby filming technology is simple, easy to operate, is well suited for suitability for industrialized production.The molecular weight of the poly ion liquid brush segmented copolymer that the present invention is prepared and the control easily that distributes thereof, the reaction conditions ratio is easier to realize, is prone to industriallization.The prepared film of this method all has good application prospects owing to have characteristics such as charged, reversible regulation and control of parent/hydrophobicity at aspects such as water treatment, sustained release, chemical sensor, fuel cells.
(3) modification of the charged PVDF blended porous membrane of intermediate ion susceptibility of the present invention employing is that hydrophobic block, poly ion liquid brush are the multipolymer of hydrophilic block with the TEB 3K; Because polymethyl acrylic acid block and PVDF have good consistency; Therefore multipolymer is difficult for from film, coming off in film process; And the water-wet behavior of poly ion liquid brush block; Make it in film process, be prone to be separated with PVDF and move to the film surface, thereby at hydrophilic, the charged menu surface layer of film surface structure.
(4) aperture of the prepared film of the present invention is 0.01 ~ 5.0 micron; Thickness is the 50-250 micron, and porosity is the flat sheet membrane of 45-80%, and the initial contact angle of film is less than 80 °; Film has tangible ion-sensitive characteristic; The contact angle of anionresin caudacoria reaches more than 100 ° in warp and the salts solution, and the size of contact angle can through with solution in anionic exchange is realized reversible regulation and control, show tangible ion-sensitive characteristic.The PVDF porous-film that the present invention is prepared is owing to have characteristics such as charged, hydrophilic; Be suitable for very much fields such as sustained release, water treatment, chemical sensor and Process Technology of Polymer; Highly charged property, the macroion electroconductibility of poly ion liquid brush make its preparation and application facet at fuel cell or lithium ion battery separator that important value all arranged simultaneously.
Embodiment
The present invention is at first through the synthetic charged block poly ion liquid multipolymer of reversible addition-fracture chain transfer polymerization (RAFT); The molecular weight of multipolymer and controllable molecular weight distribution should be used for the film blending and modifying as film properties-correcting agent (polymethylmethacrylate-g – poly ion liquid brush) by charged segmented copolymer then.Pore former is mainly used in the aperture adjustment of film in film-forming process, after water-bath film-forming and washing, pore former and solvent are all transferred in water-bath and the rinse water.
Used RAFT chain-transfer agent mainly refers to dithio RAFT reagent among the present invention; Its type mainly comprises S-1-dodecyl-S '-(α; α '-dimethyl--α " vinylformic acid) dithiocarbonates or dithiobenzoic acid isopropyl cyanide ester or dithio naphthoate etc., mainly obtain through the laboratory is synthetic.
The known compound method of following bibliographical information.
S-1-dodecyl-S '-(α; α '-dimethyl--α " vinylformic acid) dithiocarbonates synthetic reference: John T.Lai; Debby Filla; and Ronald Shea. " Functional Polymers from Novel Carboxyl-Terminated Trithiocarbonates as Highly Efficient RAFT Agents " Macromolecules 2002,35,6754-6756.The synthesized reference document of dithio naphthoate (CPDN):
Jian?Zhu,Xiulin?Zhu,Zhenping?Cheng,Feng?Liu,Jianmei?Lu.《Study?on?controlled?free-radical?polymerization?in?the?presence?of?2-cyanoprop-2-yl?1-dithionaphthalate(CPDN).》Polymer,2002,43,7037–7042。
The synthesized reference document of dithiobenzoic acid isopropyl cyanide ester (CPDB):
He Xiaoyan, Ni Gang, Bao Lili, Li Yan, Yang Wu. " reversible addition-fracture chain transfer (RAFT) radical polymerization
Preparation PMMA/SiO
2Organic/inorganic hybridization material " Northwest Normal University's journal (natural science edition), 2006,42 (2): 68-72..
Step (2) institute synthetic poly ion liquid is brushed the molecular weight of segmented copolymer (PMMA-b-PIL) 20,000 ~ 50, and 000;
Used pore former is meant that mainly molecular weight is the polyoxyethylene glycol of 200-20000;
Used pvdf, main model is Shanghai 3F (FR904), Solvay (SOLEF1015).The salts solution that blend film surface parent/hydrophobic conversion is adopted mainly contains [BF
4]
-, [PF
6]
-,-C (CF
3SO
2)
3 -,-C (C
2F
3SO
2)
3 -Etc. anionic sodium salt solution.
The characterizing method of intermediate ion susceptibility polyvinylidene fluoride porous film of the present invention mainly contains:
Polymericular weight and MWD: adopt gel permeation chromatography (Waters Co., the U.S., DMF moving phase) to measure
The measurement method of porosity of film: adopt mercury injection apparatus (DEMO AutoPore9500, the U.S.) to measure.
The surface topography of film: adopt sem (JSM-5610, Japan).
Film parent/hydrophobicity is measured: adopt the Static Water contact angle to characterize, adopt the method for dripping of lying to go up at OCA20 contact angle measurement (OCA20, German Dataphysics) and measure.
The water flux of film is measured: adopt special-purpose ultra-filtration membrane water flux determinator; At first film was soaked in pure water 12 hours during mensuration; Then film is put into the water flux determinator, earlier with film precompressed 30min under 0.15MPa, under 0.10MPa pressure, measure the water flux of film then during mensuration; Replicate(determination) three times is averaged.
To combine the embodiment of hereinafter that the present invention is done more detailed description below, but said embodiment is not construed as limiting the invention.
Embodiment 1
1. with TEB 3K (MMA), dithiocarbonates RAFT chain-transfer agent and initiator A IBN; According to [MMA]: [RAFT chain-transfer agent]: the molar ratio of [AIBN]=100:1:0.33 adds in the reactor drum; And adding proper amount of solvent 1, the 4-dioxane.Feed high-purity N while stirring
2Gas is behind the ventilation 40min, with reaction flask sealing and moved in 60 ℃ of oil baths reaction 24 hours; Then with the reaction flask quenching with termination reaction; With methyl alcohol polymer precipitation is come out, throw out to constant weight, obtains TEB 3K RAFT macromolecular chain transfer agent PMMA-R in 40 ℃ of following vacuum-dryings.
2. PMMA-R, chlorination-allyl group-3-Methylimidazole (IL) and AIBN are dissolved in the solvent DMF of nitrogen atmosphere; Wherein [PMMA-R]/[IL]=1:20, but the AIBN add-on is 0.05% of PMMA-R macromolecular chain transfer agent and ionic liquid (IL) gross weight.Behind the logical nitrogen 40min, with the reaction flask sealing and move in 60 ℃ of oil baths and react 20h, with reactant quenching and deposition, throw out is in 40 ℃ of following vacuum-drying 48h then.
3. poly ion liquid is brushed multipolymer, pvdf, PEG2000 and solvent DMF and become film-casting liquid according to certain proportional arrangement, the ratio of solid content is 18wt% in the film-casting liquid, and wherein the content of segmented copolymer is 2%, and the content of pore former is 4%.With film-casting liquid 60 ℃ of following stirring reactions 24 hours; Discontinuous degassing then; And on dull and stereotyped carrier with the nascent dull and stereotyped liquid film of scraper striking 250 μ m; And be 20 ℃ in temperature, relative humidity is to stop 20 seconds in 40% the air, the nascent liquid film on the dull and stereotyped carrier is immersed film-forming in 20 ℃ the water-bath.
4. the porous polyvinylidene blending porous membrane immersion with preparation contains [PF
6]
-Sodium-salt aqueous solution in carried out ion exchange reaction 0.5 hour, the concentration of salt is 0.5Mm, to realize hydrophilic Cl in the poly ion liquid brush
-Ion and hydrophobic to the exchange between the negatively charged ion is to change film surface parent/hydrophobicity.
The block polymer that so obtains and the performance of polyvinylidene fluoride porous film are shown in Table 1.
Embodiment 2
1. with TEB 3K (MMA), dithiocarbonates RAFT chain-transfer agent and initiator A IBN; According to [MMA]: [RAFT chain-transfer agent]: the molar ratio of [AIBN]=100:1:0.33 adds in the reactor drum; And adding proper amount of solvent 1, the 4-dioxane.Feed high-purity N while stirring
2Gas is behind the ventilation 40min, with reaction flask sealing and moved in 65 ℃ of oil baths reaction 16 hours; Then with the reaction flask quenching with termination reaction; With methyl alcohol polymer precipitation is come out, throw out to constant weight, obtains TEB 3K RAFT macromolecular chain transfer agent PMMA-R in 40 ℃ of following vacuum-dryings.
2. PMMA-R, chlorination-allyl group-3-Methylimidazole (IL) and AIBN are dissolved in the solvent DMF of nitrogen atmosphere, wherein [PMMA-R]/[IL]=1:40, the AIBN add-on is 0.1% of PMMA-R macromolecular chain transfer agent and ionic liquid (IL) gross weight.Behind the logical nitrogen 40, after just reaction flask sealed and moves into and reacts 16h in 65 ℃ of oil baths, with reactant quenching and deposition, throw out was in 40 ℃ of following vacuum-drying 48h then.
3. poly ion liquid is brushed multipolymer, pvdf, pore former PEG600 and solvent DMF and become film-casting liquid according to certain proportional arrangement, the ratio of solid content is 18wt% in the film-casting liquid, and wherein the content of segmented copolymer is 4%, and the content of pore former is 2%.With film-casting liquid 65 ℃ of following stirring reactions 16 hours; Discontinuous degassing then; And on dull and stereotyped carrier with the nascent dull and stereotyped liquid film of scraper striking 250 μ m; And be 30 ℃ in temperature, relative humidity is to stop 20 seconds in 60% the air, the nascent liquid film on the dull and stereotyped carrier is immersed film-forming in 30 ℃ the water-bath.
4. the porous polyvinylidene blending porous membrane immersion with preparation contains [PF
6]
-Sodium-salt aqueous solution in carried out ion exchange reaction 1.5 hours, the concentration of salt is 1.0mM, to realize hydrophilic Cl in the poly ion liquid brush
-Ion and hydrophobic to the exchange between the negatively charged ion is to change film surface parent/hydrophobicity.
The block polymer that so obtains and the performance of polyvinylidene fluoride porous film are shown in Table 1.
Embodiment 3
1.RAFT macromolecular chain transfer agent PMMA-R and poly ion liquid brush segmented copolymer synthetic sees embodiment 2.
2. poly ion liquid is brushed multipolymer, pvdf, pore former PEG600 and solvent DMF and become film-casting liquid according to certain proportional arrangement, the ratio of solid content is 18wt% in the film-casting liquid, and wherein the content of segmented copolymer is 6%, and the content of pore former is 2%.With film-casting liquid 70 ℃ of following stirring reactions 12 hours; Discontinuous degassing then; And on dull and stereotyped carrier with the nascent dull and stereotyped liquid film of scraper striking 250 μ m; And be 30 ℃ in temperature, relative humidity is to stop 20 seconds in 80% the air, the nascent liquid film on the dull and stereotyped carrier is immersed film-forming in 30 ℃ the water-bath.
3. the immersion with the porous polyvinylidene blending porous membrane for preparing contains [PF
6]
-Sodium-salt aqueous solution in carried out ion exchange reaction 1.5 hours, the concentration of salt is 20mM, to realize hydrophilic Cl in the poly ion liquid brush
-Ion and hydrophobic to the exchange between the negatively charged ion is to change film surface parent/hydrophobicity.
The block polymer that so obtains and the performance of polyvinylidene fluoride porous film are shown in Table 1.
Embodiment 4
1. with TEB 3K (MMA), RAFT dithiocarbonates chain-transfer agent and initiator A IBN; According to [MMA]: [RAFT chain-transfer agent]: the molar ratio of [AIBN]=100:1:0.33 adds in the reactor drum; And adding proper amount of solvent 1, the 4-dioxane.Feed high-purity N while stirring
2Gas, after the ventilation 40min, with reaction flask sealing and move into react 12 hours in 70 ℃ of oil baths after, reaction flask immersed rapidly carries out quenching in ice/water mixture with termination reaction.Then, with methyl alcohol polymer precipitation is come out, throw out to constant weight, obtains RAFT macromolecular chain transfer agent PMMA-R in 40 ℃ of following vacuum-dryings.
2. PMMA-R, bromination-(2-acryloyl-oxy six alkyl)-3-Methylimidazole (IL) and AIBN are dissolved in the solvent DMF of nitrogen; Wherein [PMMA-R]/[IL]=1:50, the AIBN add-on is 0.1% of PMMA-R macromolecular chain transfer agent and ionic liquid (IL) gross weight.With the reaction flask sealing and move in 70 ℃ of oil baths and react 20h, with reactant quenching and deposition, throw out is in 40 ℃ of following vacuum-drying 48h then behind the logical nitrogen 40min.
3. poly ion liquid is brushed multipolymer, pvdf, pore former PEG2000 and solvent DMF and become film-casting liquid according to certain proportional arrangement, the ratio of solid content is 18% in the film-casting liquid, and wherein the content of segmented copolymer is 2%, and the content of pore former is 4%.With film-casting liquid 65 ℃ of following stirring reactions 24 hours; Discontinuous degassing then; And on dull and stereotyped carrier with the nascent dull and stereotyped liquid film of scraper striking 250 μ m; And be 30 ℃ in temperature, relative humidity is to stop 30 seconds in 60% the air, the nascent liquid film on the dull and stereotyped carrier is immersed film-forming in 40 ℃ the water-bath.
4. the immersion with the porous polyvinylidene blending porous membrane for preparing contains [PF
6]
-Sodium-salt aqueous solution in carried out ion exchange reaction 2 hours, the concentration of salt is 20mM, to realize hydrophilic Br in the poly ion liquid brush
-Ion and hydrophobic to the exchange between the negatively charged ion is to change film surface parent/hydrophobicity.
The block polymer that so obtains and the performance of polyvinylidene fluoride porous film are shown in Table 1.
Embodiment 5
1. polymethylmethacrylate RAFT macromolecular chain transfer agent PMMA-R synthetic sees embodiment 4.
2. PMMA-R, chlorination-(2-acryloyl-oxy six alkyl)-3-Methylimidazole (IL) and AIBN are dissolved in the solvent DMF of nitrogen atmosphere; Wherein [PMMA-R]/[IL]=1:80, the AIBN add-on is 0.05% of PMMA-R macromolecular chain transfer agent and ionic liquid (IL) gross weight.Behind the logical nitrogen 40min with the reaction flask sealing and move in 65 ℃ of oil baths and react 24h, then with reactant quenching and deposition,, throw out is in 40 ℃ of following vacuum-drying 48h.
3. will this charged block poly ion liquid brush multipolymer, pvdf, pore former PEG2000 and solvent DMF become film-casting liquid according to certain proportional arrangement; The ratio of solid content is 18wt% in the film-casting liquid; Wherein the content of segmented copolymer is 2%, and the content of pore former is 4%.With film-casting liquid 65 ℃ of following stirring reactions 24 hours, discontinuous degassing then, and on dull and stereotyped carrier with the nascent dull and stereotyped liquid film of scraper striking 250 μ m, and be 20 ℃ in temperature, relative humidity is to stop 40 seconds in 60% the air; With film-forming in the water-bath of 40 ℃ of the nascent liquid film immersions on the dull and stereotyped carrier.
4. the immersion with 3 prepared porous polyvinylidene blending porous membranes contains [PF
6]
-Sodium-salt aqueous solution in carried out ion exchange reaction 6 hours, the concentration of salt is 30mM, to realize hydrophilic Cl in the poly ion liquid brush
-Ion and hydrophobic to the exchange between the negatively charged ion is to change film surface parent/hydrophobicity.
The block polymer that so obtains and the performance of polyvinylidene fluoride porous film are shown in Table 1.
Embodiment 6
1.RAFT the synthesis step of macromolecular chain transfer agent PMMA-R and block poly ion liquid brush multipolymer is seen embodiment 5.
2. poly ion liquid is brushed multipolymer, pvdf, pore former PEG2000 and solvent DMF and become film-casting liquid according to certain proportional arrangement, the ratio of solid content is 18wt% in the film-casting liquid, and wherein the content of segmented copolymer is 6%, and the content of pore former is 2%.With film-casting liquid 65 ℃ of following stirring reactions 16 hours, discontinuous degassing then, and on dull and stereotyped carrier with the nascent dull and stereotyped liquid film of scraper striking 250 μ m, and be film-forming in 30 ℃ the water-bath in temperature, relative humidity is to stop 40 seconds in 60% the air; With film-forming in the water-bath of 40 ℃ of the nascent liquid film immersions on the dull and stereotyped carrier.
3. the immersion with the porous polyvinylidene blending porous membrane for preparing contains [PF
6]
-Sodium-salt aqueous solution in carried out ion exchange reaction 6 hours, the concentration of salt is 40mM, to realize hydrophilic Cl in the poly ion liquid brush
-Ion and hydrophobic to the exchange between the negatively charged ion is to change film surface parent/hydrophobicity.
The block polymer that so obtains and the performance of polyvinylidene fluoride porous film are shown in Table 1.
Table 1 segmented copolymer and system film and film properties
Embodiment 7
1. with TEB 3K (MMA), dithio chain-transfer agent CPDB and initiator A IBN, according to [MMA]: [CPDB]: the molar ratio of [AIBN]=100:1:0.33 adds in the reactor drum, and adds proper amount of solvent DMF.Feed high-purity N while stirring
2Gas behind the ventilation 40min, with reaction flask sealing and moved in 60 ℃ of oil baths reaction 20 hours, immerses reaction flask rapidly and carries out quenching in ice/water mixture with termination reaction.Then, with methyl alcohol polymer precipitation is come out, throw out to constant weight, obtains RAFT macromolecular chain transfer agent PMMA-R in 40 ℃ of following vacuum-dryings.
2. PMMA-R, chlorination-(2-acryloyl-oxy six alkyl)-3-Methylimidazole (IL) and AIBN are dissolved in the solvent DMF of nitrogen atmosphere; Wherein [PMMA-R]/[IL]=1:50, the AIBN add-on is 0.1% of PMMA-R macromolecular chain transfer agent and ionic liquid (IL) gross weight.With the reaction flask sealing and move in 65 ℃ of oil baths and react 20h, with reactant quenching and deposition, throw out is in 40 ℃ of following vacuum-drying 48h then behind the logical nitrogen 40min.
3. poly ion liquid is brushed multipolymer, pvdf, pore former PEG600 and solvent DMF and become film-casting liquid according to certain proportional arrangement, the ratio of solid content is 18% in the film-casting liquid, and wherein the content of segmented copolymer is 2%, and the content of pore former is 4%.With film-casting liquid 65 ℃ of following stirring reactions 24 hours; Discontinuous degassing then; And on dull and stereotyped carrier with the nascent dull and stereotyped liquid film of scraper striking 150 μ m; And be 30 ℃ in temperature, relative humidity is to stop after 30 seconds in 60% the air, the nascent liquid film on the dull and stereotyped carrier is immersed film-forming in 30 ℃ the water-bath.
4. the porous polyvinylidene blending porous membrane immersion with preparation contains-C (C
2F
3SO
2)
3 -Sodium-salt aqueous solution in carried out ion exchange reaction 4 hours, the concentration of salt is 20mM, to realize hydrophilic Cl in the poly ion liquid brush
-Ion and hydrophobic to the exchange between the negatively charged ion is to change film surface parent/hydrophobicity.
The block polymer that so obtains and the performance of polyvinylidene fluoride porous film are shown in Table 2.
Embodiment 8
1. with TEB 3K (MMA), dithio chain-transfer agent CPDB and initiator A IBN, according to [MMA]: [CPDB]: the molar ratio of [AIBN]=100:1:0.33 adds in the reactor drum, and adds proper amount of solvent DMF.Feed high-purity N while stirring
2Gas, after the ventilation 40min, with reaction flask sealing and move into react 16 hours in 65 ℃ of oil baths after, reaction flask immersed rapidly carries out quenching in ice/water mixture with termination reaction.Then, with methyl alcohol polymer precipitation is come out, throw out to constant weight, obtains RAFT macromolecular chain transfer agent PMMA-R in 40 ℃ of following vacuum-dryings.
2. PMMA-R, chlorination-(2-acryloyl-oxy six alkyl)-3-Methylimidazole (IL) and AIBN are dissolved in the nitrogen atmosphere; And add an amount of solvent DMF; Wherein [PMMA-R]/[IL]=1:80, the AIBN add-on is 0.1% of PMMA-R macromolecular chain transfer agent and ionic liquid (IL) gross weight.With the reaction flask sealing and move in 70 ℃ of oil baths and react 20h, with reactant quenching and deposition, throw out is in 40 ℃ of following vacuum-drying 48h then behind the logical nitrogen 40min.
3. poly ion liquid is brushed multipolymer, pvdf, pore former PEG600 and solvent DMF and become film-casting liquid according to certain proportional arrangement, the ratio of solid content is 18% in the film-casting liquid, and the content of segmented copolymer is 4%, and the content of pore former is 2%.With film-casting liquid 70 ℃ of following stirring reactions 16 hours, discontinuous degassing then, and on dull and stereotyped carrier with the nascent dull and stereotyped liquid film of scraper striking 200 μ m, and be 30 ℃ in temperature, relative humidity is to stop 30 seconds in 60% the air; With film-forming in the water-bath of 40 ℃ of the nascent liquid film immersions on the dull and stereotyped carrier.
4. the porous polyvinylidene blending porous membrane immersion with preparation contains-C (CF
3SO
2)
3 -Sodium-salt aqueous solution in carried out ion exchange reaction 3 hours, the concentration of anion salt is 50mM, to realize hydrophilic Cl in the poly ion liquid brush
-Ion and hydrophobic to the exchange between the negatively charged ion is to change film surface parent/hydrophobicity.
The block polymer that so obtains and the performance of polyvinylidene fluoride porous film are shown in Table 2.
Embodiment 9
1. with TEB 3K (MMA), dithio chain-transfer agent CPDN and initiator A IBN, according to [MMA]: [RAFT chain-transfer agent]: the molar ratio of [CPDB]=100:1:0.33 adds in the reactor drum, and adds proper amount of solvent DMF.Feed high-purity N while stirring
2Gas, after the ventilation 40min, with reaction flask sealing and move into react 16 hours in 65 ℃ of oil baths after, with reaction flask immerse rapidly carry out in ice/water mixture cold with termination reaction.Then, with methyl alcohol polymer precipitation is come out, throw out to constant weight, obtains RAFT macromolecular chain transfer agent PMMA-R in 40 ℃ of following vacuum-dryings.
2. PMMA-R, chlorination-allyl group-3-Methylimidazole (IL) and AIBN are dissolved in the nitrogen atmosphere; And add in an amount of solvent DMF; Wherein [PMMA-R]/[IL]=1:80, the AIBN add-on is 0.1% of PMMA-R macromolecular chain transfer agent and ionic liquid (IL) gross weight.With the reaction flask sealing and move in 65 ℃ of oil baths and react 20h, with reactant quenching and deposition, throw out is in 40 ℃ of following vacuum-drying 48h then behind the logical nitrogen 40min.
3. poly ion liquid is brushed multipolymer, pvdf, pore former PEG2000 and solvent DMF and become film-casting liquid according to certain proportional arrangement, the ratio of solid content is 18% in the film-casting liquid, and wherein the content of segmented copolymer is 2%, and the content of pore former is 4%.With film-casting liquid 65 ℃ of following stirring reactions 24 hours, discontinuous degassing then, and on dull and stereotyped carrier with the nascent dull and stereotyped liquid film of scraper striking 250 μ m, and be 30 ℃ in temperature, relative humidity is to stop 30 seconds in 60% the air; With film-forming in the water-bath of 40 ℃ of the nascent liquid film immersions on the dull and stereotyped carrier.
4. the immersion with the porous polyvinylidene blending porous membrane for preparing contains [BF
4]
-Sodium-salt aqueous solution in carried out ion exchange reaction 4 hours, the concentration of anion salt is 40mM, to realize hydrophilic Cl in the poly ion liquid brush
-Ion and hydrophobic to the exchange between the negatively charged ion is to change film surface parent/hydrophobicity.
The block polymer that so obtains and the performance of polyvinylidene fluoride porous film are shown in Table 2.
Table 2 segmented copolymer and film forming condition and film properties
Claims (6)
1. the preparation method with charged porous polyvinylidene blending porous membrane of ion-sensitive is characterized in that comprising the steps:
(1) polymethylmethacrylate RAFT macromolecular chain transfer agent is synthetic: with MMA MONOMER, small molecules RAFT chain-transfer agent and initiator Diisopropyl azodicarboxylate; Mol ratio according to 100:1:0.33 adds in the reactor drum; And adding solvent 1, the 4-dioxane is in high-purity N
2Mixing and stirring under the gas shiled, logical N
2After the 40min; With reaction flask sealing and move in the 60-70 ℃ of oil bath reaction after 12-20 hour, reaction flask is immersed rapidly carry out quenching in ice/water mixture with termination reaction, then; With methyl alcohol polymer precipitation is come out; And clean 2-5 time repeatedly with methyl alcohol, throw out to constant weight, obtains faint yellow polymethylmethacrylate macromolecular chain transfer agent in 40 ℃ of following vacuum-dryings;
(2) charged block poly ion liquid brush multipolymer is synthetic: polymethylmethacrylate macromolecular chain transfer agent, polymerizable type imidazolium halide ionic liquid and Diisopropyl azodicarboxylate that step (1) is obtained are dissolved in the solvent DMF of nitrogen atmosphere; PMMA-R wherein: the ion liquid mol ratio of polymerizable type imidazolium halide is 1:20 ~ 1:80; The Diisopropyl azodicarboxylate add-on is the 0.05-0.1% of polymethylmethacrylate macromolecular chain transfer agent and polymerizable type imidazolium halide ionic liquid gross weight; Behind the logical nitrogen 40min with the reaction flask sealing and move in 60-70 ℃ of oil bath and react 12-24h; Back quenching and deposition, throw out obtain charged block poly ion liquid brush multipolymer more than 40 ℃ of following vacuum-drying 48h;
(3) preparation of charged porous polyvinylidene blending porous membrane: charged block poly ion liquid is brushed multipolymer, pvdf, pore former and solvent according to being configured to film-casting liquid; At 60-70 ℃ of following stirring reaction 12-24 hour; Discontinuous degassing then; And on dull and stereotyped carrier with the nascent dull and stereotyped liquid film of scraper striking 150-250 μ m, and be 20-40 ℃ in temperature, relative humidity is to stop below 40 seconds in the air of 40-80%; With film-forming in the water-bath of 20-40 ℃ of the nascent liquid film immersion on the dull and stereotyped carrier, the composition of described film-casting liquid and mass percent are: pvdf: molecular weight is 1 * 10
5~ 2 * 10
6, 10-12%; Charged block poly ion liquid brush multipolymer: 1-8%; Pore former: molecular weight is the polyoxyethylene glycol of 200-20000,2-4%; Solvent: N, dinethylformamide, DMAC N,N or N-Methyl pyrrolidone, 82%.
2. the preparation method with the charged porous polyvinylidene blending porous membrane of ion-sensitive according to claim 1; It is characterized in that described small molecules RAFT chain-transfer agent is a dithio RAFT reagent; Be selected from S-1-dodecyl-S '-(α, α '-dimethyl--α " vinylformic acid) dithiocarbonates or dithiobenzoic acid isopropyl cyanide ester (CPDB) or dithio naphthoate (CPDN).
3. the preparation method with charged porous polyvinylidene blending porous membrane of ion-sensitive according to claim 1; It is characterized in that; Described polymerizable type imidazolium halide ionic liquid (IL) is for containing allyl group (or acryloxy) the ionic liquid halide salt of different carbon chain lengths, described halogen ion X
-Be meant Br
-(or Cl
-) ion, the molecular structural formula of polymerizable type imidazole ion liquid is:
Halogenated alkenes propyl group ionic liquid halogenation acryloxy ionic liquid.
4. the preparation method with charged porous polyvinylidene blending porous membrane of ion-sensitive according to claim 1; It is characterized in that said charged block poly ion liquid brush multipolymer is for being hydrophobic segment with the polymethylmethacrylate, being the multipolymer of hydrophilic block with the poly ion liquid brush.
5. the preparation method with charged porous polyvinylidene blending porous membrane of ion-sensitive according to claim 1; It is characterized in that; Step (3) gained blended porous membrane is carried out parent/hydrophobic conversion through film to anionresin; Be about to prepared blend film and immerse in the salt brine solution that the different concns negatively charged ion forms and carry out, to realize hydrophilic Br in the poly ion liquid brush ion exchange reaction 0.5-6 hour
-(or Cl
-) ion and hydrophobic to the exchange between the negatively charged ion, selected commutative be [BF to ion
4]
-, [PF
6]
-,-C (CF
3SO
2)
3 -, or-C (C
2F
3SO
2)
3 -, the concentration of salt brine solution is 0.5-50mM.
6. a claim 1 is described has a charged porous polyvinylidene blending porous membrane of ion-sensitive; It is characterized in that this film is made by the said preparation method of claim 1, the aperture of film is 0.01 ~ 5.0 micron, and thickness is the 50-250 micron; Porosity is the flat sheet membrane of 45-80%; The film initial contact angle is less than 80 °, and the film surface has ion-sensitive, reaches more than 100 ° with anionresin caudacoria surface contact angle in the salts solution.
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| CN106084260A (en) * | 2016-06-14 | 2016-11-09 | 吉林市润成膜科技有限公司 | A kind of preparation method of PVDF adsorbed film |
| CN106084260B (en) * | 2016-06-14 | 2018-10-23 | 吉林市润成膜科技有限公司 | A kind of preparation method of PVDF adsorbed films |
| CN109370122B (en) * | 2018-09-12 | 2021-02-09 | 济南大学 | Preparation method of polyvinylidene fluoride/modified barium titanate composite film |
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| CN111617641A (en) * | 2020-05-07 | 2020-09-04 | 天津工业大学 | Imidazole functionalized ionic liquid copolymer synthesis and alloy ultrafiltration membrane preparation method |
| CN111617641B (en) * | 2020-05-07 | 2021-12-10 | 天津工业大学 | Imidazole functionalized ionic liquid copolymer synthesis and alloy ultrafiltration membrane preparation method |
| CN112479303A (en) * | 2020-12-16 | 2021-03-12 | 咸阳职业技术学院 | Sewage catalytic unit based on porous polyion liquid |
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