CN104084057B - A kind of preparation method of diffusion dialysis cation-exchange membrane - Google Patents
A kind of preparation method of diffusion dialysis cation-exchange membrane Download PDFInfo
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- CN104084057B CN104084057B CN201410364509.4A CN201410364509A CN104084057B CN 104084057 B CN104084057 B CN 104084057B CN 201410364509 A CN201410364509 A CN 201410364509A CN 104084057 B CN104084057 B CN 104084057B
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Abstract
The invention discloses a kind of preparation method of diffusion dialysis cation-exchange membrane, it is characterized in that: will containing double bond and-SO
3the monomer of Na group obtains polyelectrolyte by electro transfer activating and regenerating catalyst atoms transferring free-radical polymerization (ARGET-ATRP), by this polyelectrolyte and film matrix polyvinyl alcohol blending, and obtaining coating liquid with silane coupler is crosslinked, dry after film, heat treatment obtains cation-exchange membrane.The performances such as coating liquid good film-forming property, film pliability are good, tear-proof that method of the present invention utilizes the toughness of polyvinyl alcohol and intensity to give; The great amount of hydroxy group (-OH) utilizing PVA to contain and high-hydrophilic give film to hydrated ion as OH
-high dialysis flux; By adding of polyelectrolyte, ion-exchange group is introduced in film, give film Thief zone amount, ion selection stalling characteristic; Recycle silicon alkane is cross-linked, and can overcome the shortcoming that film swellbility is high.
Description
Technical field
The invention belongs to amberplex preparing technical field, particularly polyelectrolyte preparation, the method that blended, crosslinked with silicane prepares diffusion dialysis cation-exchange membrane.
Background technology
A large amount of spent acid salkali waste can be produced, if without suitably process directly discharge, the useful resources in waste liquid not only effectively cannot be utilized, also can cause serious infringement to environment and water source, biology in modern industry production process.Ionic membrane is applied to diffusion dialysis (DD), can be effectively separated and waste acid recovery salkali waste.DD process, only using film both sides feed liquid concentration difference as driving force, has continuous, simple, efficient and features such as economic environmental protection.DD process spent acid, needs anion-exchange membrane; Process salkali waste, needs cation-exchange membrane.These two kinds of ionic membranes are all generally with polyphenylene oxide, polystyrene, polysulfones, polyether sulfone etc. for parent, because of its main body comparatively hydrophobic, so very little to the dialysis flux of acid or alkali.In acid recovery, periodical " JournalofMembraneScience " 347 volume 240-249 pages in 2010 report commercial anionic exchange membrane (DF-120) in static DD process, to the dialysis flux of HCl in 0.002-0.009m/h scope; Periodical " China YouSe Acta Metallurgica Sinica " 18 volume 88-91 pages in 2008 are reported in dynamic DD process, 500m
2polyphenylene oxide (PPO) the anion-exchange membrane acid solution treating capacity of a day only about 6 tons.In alkali collection, due to OH
-migratory activity is significantly lower than H
+, the migration velocity in film is more slow, so dialysis flux is lower.Current DD is used for the industrialization of alkali collection and research reports that comparatively much less is wanted in acid recovery, wherein periodical " JournalofMembraneScience " the 347th volume 240-249 page in 2010 reports PPO commercial cationic exchange membrane in static DD process, is only about 0.0014m/h to the dialysis flux of NaOH.Periodical " membrane science and technology " calendar year 2001 21 volume 37-43 page reports such film for dynamic DD process, and the treating capacity of a day is estimated less than 1 ton, can not be applied to actual separation occasion.Integrate and see, existing amberplex, particularly cation-exchange membrane also exist obvious defect and deficiency in DD process salkali waste.For this reason, the cation-exchange membrane preparing high dialysis flux is needed.In addition, the longtime running of DD also needs film to have higher stability.
Polyvinyl alcohol (PVA) is a kind of macromolecular material with excellent hydrophily, stain resistance and filming performance, and the higher and environmental friendliness of its mechanical performance, heat endurance and chemical stability, is commonly used to the active cortex as composite membrane at present.Containing a large amount of hydroxyls (-OH) in PVA, hydrophily is high, little to the osmotic resistance of hydrated ion, and can promote H by hydrogen bond action
+and OH
-the transmission of ion, institute is for having good dialysis flux in DD process.But the hydrophily of PVA and a large amount of-OH group also make its water-swellable strengthen, and cause the stability of film, selective decline, in actual applications cannot stable for extended periods of time simultaneously.On the other hand owing to not containing ion-exchange group in PVA, so directly DD field cannot be used for as ionic membrane.
In order to improve the stability of PVA, existing researcher carries out cross-linking modified with aldehyde to PVA.Periodical " membrane science and technology " 20 volume 23-25 page report glyoxals, glutaraldehyde, terephthalaldehyde in 2000 are cross-linked PVA and polyacrylonitrile compound film, are separated alcohol/water for infiltration evaporation.The toxicity of aldehyde is larger, and when crosslinking degree increases, the flux of film declines, this is because namely aldehyde is cross-linked is hydroxyl generation aldolisation in aldehyde and PVA, so the hydroxyl in PVA significantly can be consumed, make to rely on hydrogen bond between macromolecular chain and the interaction that occurs weakens.
On the other hand, in order to introduce ion-exchange group in PVA film, have researcher by PVA and polystyrolsulfon acid (PSS) or kayexalate (PSSNa) blended.Periodical " JournalofAppliedPolymerScience " 88 volume 79-87 pages in 2003 utilize the blended obtained evenly pliable and tough film of PVA and PSSNa, and this film has good electric conductivity and mechanical performance.But because film is cross-linked, so the swellability of film does not effectively overcome, cannot water treatment field be used for.Periodical " JournalofMembraneScience " 463 volume 173-182 pages in 2014 report PVA and PSSNa is blended and are cross-linked with glutaraldehyde, are coated in porous polysulfones (PSf) membrane surface and obtain composite membrane.In this composite membrane, PVA-PSSNa is only as superficial cortical layers, and film main body is still the limited efficiency of hydrophobicity film, improvement.In addition, aldehyde crosslinking method can consume the hydroxyl in PVA equally.So film is mainly used as nanofiltration, be not suitable for DD field.Periodical " SolidStateIonics " 253 volume 189-194 pages in 2013 by PVA and polystyrolsulfon acid (PSS) blended, and to be cross-linked with succinic acid (SA) at 180-200 DEG C.Under the catalysis of acid, PVA carries out dehydration condensation and generates double bond and ehter bond, reaches cross-linking effect.But crosslinked caudacoria becomes fine and close, and PVA chain pliability reduces, and hydroxyl loss is more.This kind of film is used for fuel cell mainly as proton conductive membrane, is not suitable for DD field.
DD field is used successfully in order to make PVA, periodical " Desalination " 304 volume 25-32 pages in 2012 describe by SSNa and γ-methacryloxypropyl trimethoxy silane (KH570) by free-radical polymerized obtained many siliceous copolymers, then by PVA and the blended masking of many siliceous copolymers.This film may be used for DD process NaOH/Na
2wO
4mixed liquor, reaches higher alkali dialysis flux (0.0102-0.0111m/h) and separation factor (16.9-18.5).Because SSNa contains-SO
3na group is ionic comonomer, so comparatively large with the difficulty of KH570 copolymerization, product structure and molecular weight cannot accurately control, and molecular weight is lower.In addition, the KH570 composition also containing nonionic in many siliceous copolymers, so compared with PSSNa, ion exchange capacity is lower.More crucially, hold concurrently in many siliceous copolymers containing a large amount of-SO
3na and-Si (OR)
3group ,-SO in polymerization and preservation process
3na can catalysis-Si (OR)
3hydrolysis, condensation, so easily self intersection connection forms gel, preparation and store difficulty, is unfavorable for amplifying and produces.
Summary of the invention
The present invention is intended to make up above-mentioned deficiency, provides a kind of preparation method of cation-exchange membrane, and technical problem to be solved how to prepare high, the selective good and diffusion dialysis cation-exchange membrane that good stability, swellability are low of dialysis flux.
Technical solution problem of the present invention, adopts following technical scheme:
The preparation method of diffusion dialysis cation-exchange membrane of the present invention, its feature is: will containing double bond and-SO
3the monomer of Na group carries out electro transfer activating and regenerating catalyst atoms transferring free-radical polymerization (ARGET-ATRP), obtains polyelectrolyte; By evenly blended for the aqueous solution of described polyelectrolyte and film matrix polyvinyl alcohol (PVA), then add silane coupler and be cross-linked, obtain coating liquid; By described coating liquid film, then carry out drying, heat treatment, obtain cation-exchange membrane.
Preparation method of the present invention, its feature is also:
Will containing double bond and-SO
3the monomer of Na group carries out electro transfer activating and regenerating catalyst atoms transferring free-radical polymerization, and to obtain polyelectrolyte be carry out as follows:
Step 1: add solvent in polymerization pipe, by initator, catalyst, part and containing double bond and-SO
3the monomer of Na group is dissolved in described solvent, then in described polymerization pipe, passes into inert gas, bubbling 1-2h;
Step 2: reactant in polymerization pipe is refrigerated to solid-state, being then evacuated to vacuum in polymerization pipe is 0.05-100Pa, and keeps 2-5min, then pass into inert gas return to normal pressure keep 3min, finally reactant in polymerization pipe is thawed to liquid state;
Step 3: repeat step 2 twice again;
Step 4: add reducing agent again in polymerization pipe; and described in inert gas shielding lower seal polymerization pipe, at 60-120 DEG C stir polymerization 12-48h, stop polymerization; by product in polymerization pipe successively through precipitation, centrifugal, 60 DEG C be dried to constant weight, obtain polyelectrolyte.
Solvent described in step 1 is the mixed solvent that the first alcohol and water of dimethyl sulfoxide (DMSO) or 1:1 mixing is by volume formed; Described initator is selected from bromoethyl acetate (EBrA), alpha-brominated ethyl butyrate (EBrB) or alpha-brominated ethyl isobutyrate (EBiB); Described catalyst is selected from copper bromide (CuBr
2), copper chloride (CuCl
2) or iron chloride (FeCl
3); Described part be selected from bipyridine (bpy), N, N, N ', N ', N "-five methyl diethylentriamine (PMEDTA) or three-(N, N-dimethylaminoethyl) amine (Me
6tREN); Described containing double bond and-SO
3the monomer of Na group is SSS (SSNa);
Reducing agent described in step 4 is selected from ascorbic acid (AsAc), hydrazides or stannous octoate;
The mol ratio of described initator, catalyst, part and monomer is 20-50:1:50:200-800; The quality of described monomer and the volume ratio of described solvent are 1g:10-40ml; The mol ratio of described catalyst and described reducing agent is 1:5-10.
Described inert gas is selected from argon gas, nitrogen or helium;
Being refrigerated to by reactant in polymerization pipe solid-state in step 2 is be cooled to by reactant in polymerization pipe to be transformed into solid completely by liquid below-100 DEG C;
In step 2, reactant in polymerization pipe is thawed to liquid state be polymerization pipe is placed on 10-40 DEG C at, until reactant is liquid by solid-state thawing completely in polymerization pipe;
Stop polymerization to be broken by the polymerization pipe sealed described in step 4, reactant in polymerization pipe is exposed in atmosphere, polymerization is stopped.
Precipitation described in step 4 is added drop-wise to by the product in polymerization pipe in precipitating reagent to form precipitation; Described precipitating reagent is selected from oxolane (THF) or absolute ether.
The mass ratio of described polyelectrolyte and described film matrix polyvinyl alcohol is 0.5-1.5:1; Be: first prepare the aqueous solution that mass concentration is the film matrix polyvinyl alcohol of 5% then described polyelectrolyte at room temperature to be joined the blended uniform step of the aqueous solution of described polyelectrolyte and film matrix polyvinyl alcohol in the aqueous solution of described film matrix polyvinyl alcohol and to stir 15-30min.
The mass ratio of described polyelectrolyte and described silane coupler is 1:1-2.5; Described silane coupler is selected from γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane (KH560), tetraethoxysilane (TEOS), (3-aminopropyl) triethoxysilane (A-1100) or γ-methacryloxypropyl trimethoxy silane (KH570); Described being cross-linked is at 25-60 DEG C of stirring reaction 20min-6h.
Described film is coated on polyfluortetraethylene plate by described coating liquid;
Described drying be the polyfluortetraethylene plate being coated with coating liquid is placed in air circulation place until coating liquid exsiccation film forming, film is taken off from tetrafluoroethene plate;
Described heat treatment is that the film taken off from polyfluortetraethylene plate is first heated 0.5-2h at 30-60 DEG C, then with the ramp of 5-20 DEG C/h to 120-140 DEG C, and be incubated 2-5h.
Compared with the prior art, beneficial effect of the present invention is embodied in:
The present invention is by blended for PVA and polyelectrolyte PSSNa, PVA has that hydrophily is high, stain resistance is high, filming performance is good, mechanical performance, heat endurance and chemical stability advantages of higher, a large amount of-OH group is contained in addition in PVA, this group belongs to high-hydrophilic group, and can form hydrogen bond between-OH group, can promote OH in DD process
-transport, cause it in DD process, have good dialysis flux, this just meet DD reclaim alkali lye to the requirement of dialysis flux; Because PSSNa contains ion-exchange group-SO
3na, introduces in PVA film by PSSNa, just impart high selective of film;
The present invention adopts silane coupler to be cross-linked PVA and PSSNa blend film first, and it is large that conventional aldehyde is cross-linked toxicity, and significantly consumes-OH the base in PVA; Silane coupler can be hydrolyzed, condensation, self forms Si-O-Si inorganic network, can also be cross-linked by Si-O-C key and PVA forming section, thus erect between inorganic substances and the interface of organic substance " molecular bridge ", improve the stability of film, solvent resistance, overcome the shortcoming that PVA film swellability is high; The Si-OH that silane hydrolyzate generates can make up the part consumption of-OH group in PVA, also promotes hydration OH in DD process
-the transmission of ion, thus keep film to the permeation flux of alkali;
The present invention adopts ARGET-ATRP to prepare PSSNa, compared with radical polymerization, can obtain more regular product structure and the molecular weight of Geng Gao, in addition, not containing-Si (OR) in PSSNa
3group, so not easily self intersection connection forms gel, can preserve for a long time, this point is produced significant to amplification.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of the cation-exchange membrane that the embodiment of the present invention 1 prepares;
Fig. 2 is the Thermal Chart of the cation-exchange membrane that the embodiment of the present invention 1 prepares;
Fig. 3 is the Thermal Chart of reference film 2 in the embodiment of the present invention 2;
Fig. 4 is the infrared spectrogram of the cation-exchange membrane that the embodiment of the present invention 3 prepares;
Fig. 5 is the Thermal Chart of the cation-exchange membrane that the embodiment of the present invention 3 prepares;
Fig. 6 is the infrared spectrogram of the cation-exchange membrane that the embodiment of the present invention 4 prepares;
Fig. 7 is the Thermal Chart of the cation-exchange membrane that the embodiment of the present invention 4 prepares.
Detailed description of the invention
Further describe the preparation method of subject cationic exchange membrane by the following examples.
Embodiment 1:
The present embodiment prepares diffusion dialysis cation-exchange membrane through following steps:
1, by the SSS (SSNa) purchased with ethanol/water (volume ratio of ethanol and water is for 9:1) for solvent recrystallization is purified.30ml methanol-water solution (volume ratio 1:1) is added in polymerization pipe.Continue to add the alpha-brominated ethyl isobutyrate of 0.430ml (EBiB), 0.0034g copper bromide (CuBr
2), 0.156mlN, N, N ', " above four kinds of material mol ratios are 20:1:50:700, are mixed to solid and dissolve completely for-five methyl diethylentriamine (PMDETA), 2gSSNa, after liquid clarification is homogeneous, pass into 1h nitrogen, bubbling deoxygenation for N ', N.
By polymerization pipe with-198 DEG C of liquid nitrogen frozens until in pipe reactant be all transformed into solid by liquid, then use vacuum pump evacuation, until vacuum is 0.06Pa, keep 3min.Passing into nitrogen again to recovering normal pressure, keeping 3min, finally thawing at 25 DEG C again, until solid is melted into liquid completely.Continuation liquid nitrogen frozen, so after three " freezing-to vacuumize-Tong nitrogen-thaw " cyclic processes, can remove the oxygen in reactant.
The ascorbic acid (AsAc) of 0.013g is added, CuBr in polymerization pipe
2and the molar ratio between AsAc is 1:5.Seal polymerization pipe under nitrogen protection, be placed in 80 DEG C of oil bath pan stirring reactions, break polymerization pipe after 24h, reactant in polymerization pipe is exposed in atmosphere, and reaction stops.Product in tube sealing is added drop-wise to precipitation in oxolane (THF), goes out product by centrifuge and be placed in 60 DEG C of baking ovens to be dried to constant weight, namely obtain polyelectrolyte PSSNa.
2, PVA is mixed with the homogeneous aqueous solution of 5% (mass concentration), gets 0.5gPSSNa and at room temperature join in 20mlPVA solution, after stirring 20min, obtain the solution of homogeneous clarification.
3,1g tetraethoxysilane (TEOS) is joined in the uniform solution of above polyelectrolyte and PVA, be placed in 60 DEG C of oil bath pan magnetic agitation 6h, obtain homogeneous coating liquid.Coating liquid is coated on polyfluortetraethylene plate, is placed in fume hood inner drying film forming, intactly film is taken off.By film first at 60 DEG C of heating 1h, then with the ramp to 130 DEG C of 10 DEG C/h, keep 4h, obtain cation-exchange membrane.
In addition, get the PVA aqueous solution of 20ml5% as coating liquid, pass through and film similar above, dry run, obtain PVA blank film.This blank film is through formaldehyde crosslinking, and the film obtained is as reference film 1.Wherein formaldehyde crosslinking is immersed in by film containing 5.41g formaldehyde, in the mixed solution of 12.5g sulfuric acid and 47g water, in 60 DEG C of reaction 2h.
The mean molecule quantity being tested polyelectrolyte PSSNa by GPC is 5310, and polydispersity index PDI value is 1.55.Periodical " Desalination " 304 volume 25-32 pages in 2012 carry out free-radical polymerized to SSNa and KH570, many siliceous copolymers obtained and PVA is blended prepares DD film, but do not report the molecular weight of many siliceous copolymers.As a comparison, periodical " JournalofMembraneScience " 399-400 phase 16-27 pages report p-chloromethyl styrene (VBC) in 2012 and KH570 carry out free-radical polymerized, wherein VBC is not containing ion-exchange group, so copolymerization difficulty should comparatively SSNa be low, but copolymerization product is just obviously divided into solid and liquid two-phase in precipitation, purification process, there were significant differences for two-phase molecular weight, is respectively 3565 and 733.By contrast, illustrate that PSSNa prepared by the present embodiment has higher molecular weight, molecular weight distribution is also more regular.
Cation-exchange membrane and reference film 1 are carried out to diffusion dialysis (DD) test process of alkali: film is immersed in 1.0mol/LNaOH and 0.1mol/LNa
2wO
42h in mixed solution, then spends deionized water, loads in static diffusion dialysis (DD) device.Film side is 100mlNaOH (1.0mol/L) and Na
2wO
4(0.1mol/L) mixed solution, opposite side is 100ml deionized water.In order to reduce the impact of concentration polarization, the speed that two Room are stirred keeps identical, sampling and testing after 1h.OH in solution
-ion concentration HCl titration method measures, WO
4 2-ion concentration rhodanate metric measurement.In above process, DD device and method of testing are with reference to periodical literature " SeparationandPurificationTechnology " 115 volume 216-223 page reports in 2013.
In addition, cation-exchange membrane is carried out infrared, thermal analyses test, and carry out water content, ion exchange capacity test, result is as follows.
The infrared spectrum of the cation-exchange membrane of Fig. 1 prepared by the present embodiment, in figure, ~ 3450cm
-1for the vibration performance peak of the upper-OH of PVA or-Si-OH, ~ 2940cm
-1for-CH
2absworption peak, ~ 1648cm
-1-CH
3,-CH
2-, the stretching vibration peak of=CH-group, ~ 1120cm
-1it is the stretching vibration peak of-Si-O-Si-.~ 1040cm
-1with ~ 1200cm
-1-SO
3the stretching vibration peak of Na.This shows that PVA and PSSNa success is blended, and silane TEOS also serves effective crosslinked action.
The Thermal Chart of the cation-exchange membrane of Fig. 2 prepared by the present embodiment, under result shows air atmosphere, cation-exchange membrane heat decomposition temperature (Td, temperature when weightless 5%) is 118.6 DEG C.
Water content test shows that cation-exchange membrane water content is 120.7%.
Ion exchange capacity measurement result: cation exchange capacity is 1.24mmol/g.As a comparison, periodical " Desalination " 2012 304 volume 25-32 page report PVA and the blended films obtained of many siliceous copolymers, its cation exchange capacity is 0.72-1.05mmol/g.
DD result shows: cation-exchange membrane is to OH
-ionodialysis flux is 0.0208m/h, and separation factor is 18.41.Reference film 1 couple of OH
-ionodialysis flux is 0.0080m/h, and separation factor is 9.25.
The above analysis result, the cation-exchange membrane that known the present embodiment obtains, has higher ion exchange capacity, hydrophily and heat endurance.Compared to reference film 1, this film is used for DD NaOH separating/Na
2wO
4time, dialysis flux and separation selectivity significantly improve, and illustrate that the PSSNa's containing ion-exchange group adds the dialysis flux and separation selectivity that can significantly improve film.
Embodiment 2
The preparation method of the present embodiment cation-exchange membrane is with embodiment 1, and blended unlike the PVA aqueous solution getting 1gPSSNa and 20ml5%, namely the mass ratio of PSSNa and PVA is 1:1; Get 1.0608g (3-aminopropyl) triethoxysilane (A-1100) as silane coupler, replace 1.0gTEOS, be cross-linked with the uniform solution of polyelectrolyte, PVA; Cross-linking reaction time shortens to 2h, obtains cation-exchange membrane.
For ease of contrast, take and upper similar process, but replace silane coupler to be cross-linked with formaldehyde crosslinking, obtain reference film 2.Wherein, formaldehyde crosslinking process is similar to the respective process of reference film 1 in embodiment 1.
The cation-exchange membrane obtained the present embodiment carries out water content and hot water swelling power can test.Water content test shows: water content is 54.83%.Hot water swelling power's test shows: the swellbility of 108h caudacoria is 52.75%.Carry out thermal analyses test to reference film 2, Fig. 3 is the Thermal Chart of the present embodiment reference film 2, and under result shows air atmosphere, the heat decomposition temperature (Td, temperature when weightless 5%) of film is only 35.25 DEG C.
Analyze above-mentioned experimental result, the film that known the present embodiment obtains, water content is suitable for, and swellbility is low, and still very low through reference film 2 heat endurance of formaldehyde crosslinking, does not improve.In sum, PSSNa-PVA film after A-1100 is crosslinked, swellbility and stability be improved significantly.
Embodiment 3
The present embodiment preparation method, with embodiment 1, replaces 1gTEOS as silane coupler unlike by 1.1345g γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane (KH560); Crosslinking time shortens to 20min, obtains cation-exchange membrane.Infrared, water content, thermal analyses, ion exchange capacity and DD test is carried out to this film.
The infrared spectrum of the cation-exchange membrane of Fig. 4 prepared by the present embodiment, in figure, ~ 3450cm
-1for the vibration performance peak of the upper-OH of PVA or-Si-OH, ~ 2940cm
-1for-CH
2absworption peak, ~ 1650cm
-1-CH
3,-CH
2-, the stretching vibration peak of=CH-group, ~ 1120cm
-1it is the stretching vibration peak of-Si-O-Si-.~ 1040cm
-1with ~ 1201cm
-1-SO
3the stretching vibration peak of Na.This shows that PVA and PSSNa success is blended, and silane KH560 also serves effective crosslinked action.
The Thermal Chart of the cation-exchange membrane of Fig. 5 prepared by the present embodiment, under result shows air atmosphere, film heat decomposition temperature Td is 150 DEG C.
Water content test shows: water content is 46.85%.
The cation exchange capacity that ion exchange capacity measures film is 1.64mmol/g, is significantly higher than the respective value (0.72-1.05mmol/g) of the film of periodical " Desalination " 304 volume 25-32 page reports in 2012.
Diffusion dialysis result shows: film is to OH
-ionodialysis flux is 0.014m/h, and separation factor is 25.72.As a comparison, periodical " SeparationandPurificationTechnology " the 115th volume 216-223 page in 2013 reports PPO commercial cationic exchange membrane to OH
-ionodialysis flux is 0.007m/h, and separation factor is 11.
The above analysis result, the cation-exchange membrane that known the present embodiment obtains, has higher ion exchange capacity, and the water content of film is suitable.Relative to PPO commercial membranes, this film is used for DD NaOH separating/Na
2wO
4excellent dialysis flux and separation selectivity can be obtained, illustrate that film can effectively improve its application performance through crosslinked with silicane.
Embodiment 4
The present embodiment preparation method, with embodiment 1, replaces 1gTEOS as silane coupler unlike using 1.0608gA-1100; Crosslinking time is 2h.
Infrared, water content, thermal analyses, ion exchange capacity and DD test is carried out to the cation-exchange membrane that the present embodiment obtains.
The infrared spectrum of the cation-exchange membrane of Fig. 6 prepared by the present embodiment, in figure, ~ 3450cm
-1for the vibration performance peak of the upper-OH of PVA or-Si-OH, ~ 2940cm
-1for-CH
2absworption peak, ~ 1665cm
-1-CH
3,-CH
2-, the stretching vibration peak of=CH-group, ~ 1125cm
-1it is the stretching vibration peak of-Si-O-Si-.~ 1040cm
-1with ~ 1198cm
-1-SO
3the stretching vibration peak of Na.This shows that PVA and PSSNa success is blended, and silane A-1100 also serves effective crosslinked action.
The Thermal Chart of the cation-exchange membrane of Fig. 7 prepared by the present embodiment, under result shows air atmosphere, film heat decomposition temperature (Td, temperature when weightless 5%) is 112 DEG C.
Water content test shows: water content is 55.22%.
The cation exchange capacity that ion exchange capacity measures film is 1.03mmol/g.
Diffusion dialysis result shows: cation-exchange membrane is to OH
-ionodialysis flux is 0.0072m/h, and separation factor is 16.77.
The above analysis result, the cation-exchange membrane that known the present embodiment obtains, ion exchange capacity is higher, and the water content of film is suitable.When this film is used for alkali DD, dialysis flux and separation selectivity are lower than embodiment 1 and 3, but still are better than business PPO film, illustrate that film can effectively improve its application performance through crosslinked with silicane.
Claims (5)
1. a preparation method for diffusion dialysis cation-exchange membrane, is characterized in that: will containing double bond and-SO
3the monomer of Na group carries out electro transfer activating and regenerating catalyst atoms transferring free-radical polymerization, obtains polyelectrolyte; By evenly blended for the aqueous solution of described polyelectrolyte and film matrix polyvinyl alcohol, then add silane coupler and be cross-linked, obtain coating liquid; By described coating liquid film, then carry out drying, heat treatment, obtain cation-exchange membrane;
Will containing double bond and-SO
3the monomer of Na group carries out electro transfer activating and regenerating catalyst atoms transferring free-radical polymerization, and to obtain polyelectrolyte be carry out as follows:
Step 1: add solvent in polymerization pipe, by initator, catalyst, part and containing double bond and-SO
3the monomer of Na group is dissolved in described solvent, then in described polymerization pipe, passes into inert gas, bubbling 1-2h;
Step 2: reactant in polymerization pipe is refrigerated to solid-state, being then evacuated to vacuum in polymerization pipe is 0.05-100Pa, and keeps 2-5min, then pass into inert gas return to normal pressure keep 3min, finally reactant in polymerization pipe is thawed to liquid state;
Step 3: repeat step 2 twice again;
Step 4: add reducing agent again in polymerization pipe, and described in inert gas shielding lower seal polymerization pipe, at 60-120 DEG C stir polymerization 12-48h, stop polymerization, by product in polymerization pipe successively through precipitation, centrifugal, 60 DEG C be dried to constant weight, obtain polyelectrolyte;
The mass ratio of described polyelectrolyte and described film matrix polyvinyl alcohol is 0.5-1.5:1; Be: first prepare the aqueous solution that mass concentration is the film matrix polyvinyl alcohol of 5% then described polyelectrolyte at room temperature to be joined the blended uniform step of the aqueous solution of described polyelectrolyte and film matrix polyvinyl alcohol in the aqueous solution of described film matrix polyvinyl alcohol and to stir 15-30min;
The mass ratio of described polyelectrolyte and described silane coupler is 1:1-2.5; Described silane coupler is selected from γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, tetraethoxysilane, (3-aminopropyl) triethoxysilane or γ-methacryloxypropyl trimethoxy silane; Described being cross-linked is at 25-60 DEG C of stirring reaction 20min-6h.
2. preparation method according to claim 1, is characterized in that:
Solvent described in step 1 is the mixed solvent that the first alcohol and water of dimethyl sulfoxide (DMSO) or 1:1 mixing is by volume formed; Described initator is selected from bromoethyl acetate, alpha-brominated ethyl butyrate or alpha-brominated ethyl isobutyrate; Described catalyst is selected from copper bromide, copper chloride or iron chloride; Described part is selected from bipyridine, N, N, N', N', N "-five methyl diethylentriamine or three-(N, N-dimethylaminoethyl) amine; Described containing double bond and-SO
3the monomer of Na group is SSS;
Reducing agent described in step 4 is selected from ascorbic acid, hydrazides or stannous octoate;
The mol ratio of described initator, catalyst, part and monomer is 20-50:1:50:200-800; The quality of described monomer and the volume ratio of described solvent are 1g:10-40ml; The mol ratio of described catalyst and described reducing agent is 1:5-10.
3. preparation method according to claim 1, is characterized in that:
Described inert gas is selected from argon gas, nitrogen or helium;
Being refrigerated to by reactant in polymerization pipe solid-state in step 2 is be cooled to by reactant in polymerization pipe to be transformed into solid completely by liquid below-100 DEG C;
In step 2, reactant in polymerization pipe is thawed to liquid state be polymerization pipe is placed on 10-40 DEG C at, until reactant is liquid by solid-state thawing completely in polymerization pipe;
Stop polymerization to be broken by the polymerization pipe sealed described in step 4, reactant in polymerization pipe is exposed in atmosphere, polymerization is stopped.
4. preparation method according to claim 1, is characterized in that:
Precipitation described in step 4 is added drop-wise to by the product in polymerization pipe in precipitating reagent to form precipitation; Described precipitating reagent is selected from oxolane or absolute ether.
5. preparation method according to claim 1, is characterized in that:
Described film is coated on polyfluortetraethylene plate by described coating liquid;
Described drying be the polyfluortetraethylene plate being coated with coating liquid is placed in air circulation place until coating liquid exsiccation film forming, film is taken off from tetrafluoroethene plate;
Described heat treatment is that the film taken off from polyfluortetraethylene plate is first heated 0.5-2h at 30-60 DEG C, then with the ramp of 5-20 DEG C/h to 120-140 DEG C, and be incubated 2-5h.
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| CN108654394B (en) * | 2018-05-29 | 2020-08-25 | 南京林业大学 | Nanofiber cation exchange membrane and preparation method and application thereof |
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| CN113368697B (en) * | 2021-04-07 | 2022-05-17 | 中国海洋大学 | Monovalent cation selective separation membrane modified by metal organic framework material and preparation method and application thereof |
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