CN1973972A - Prepn process of reinforced hybrid organic-inorganic film - Google Patents
Prepn process of reinforced hybrid organic-inorganic film Download PDFInfo
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- CN1973972A CN1973972A CN 200610144296 CN200610144296A CN1973972A CN 1973972 A CN1973972 A CN 1973972A CN 200610144296 CN200610144296 CN 200610144296 CN 200610144296 A CN200610144296 A CN 200610144296A CN 1973972 A CN1973972 A CN 1973972A
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- 230000008569 process Effects 0.000 title description 7
- 238000005266 casting Methods 0.000 claims abstract description 56
- 238000002360 preparation method Methods 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 229920000620 organic polymer Polymers 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 239000000654 additive Substances 0.000 claims abstract description 15
- 230000000996 additive effect Effects 0.000 claims abstract description 15
- 238000009987 spinning Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 40
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 39
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 35
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 30
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 30
- 229920002492 poly(sulfone) Polymers 0.000 claims description 29
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 26
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 26
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 26
- 238000007766 curtain coating Methods 0.000 claims description 23
- 230000001112 coagulating effect Effects 0.000 claims description 21
- 239000002202 Polyethylene glycol Substances 0.000 claims description 19
- 229920001223 polyethylene glycol Polymers 0.000 claims description 19
- 229920001721 polyimide Polymers 0.000 claims description 19
- 239000004642 Polyimide Substances 0.000 claims description 18
- 239000004800 polyvinyl chloride Substances 0.000 claims description 16
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 9
- 239000004695 Polyether sulfone Substances 0.000 claims description 8
- 229920006393 polyether sulfone Polymers 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 5
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 4
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 abstract description 12
- 238000007711 solidification Methods 0.000 abstract 2
- 230000008023 solidification Effects 0.000 abstract 2
- 239000010408 film Substances 0.000 description 112
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 29
- 239000002033 PVDF binder Substances 0.000 description 21
- 239000011701 zinc Substances 0.000 description 21
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 16
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
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- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- Manufacture Of Macromolecular Shaped Articles (AREA)
- Moulding By Coating Moulds (AREA)
Abstract
The present invention is preparation process of reinforced hybrid organic-inorganic film and belongs to the field of organic-inorganic separating film preparing technology. During the preparation of the reinforced hybrid organic-inorganic film, inorganic precursor is added directly into filming liquid of organic polymer to obtain the mixture film casting liquid comprising organic polymer 10-20 wt%, additive 0-10 wt%, solvent 55-80 wt% and inorganic precursor 0-24 wt%; the film casting liquid is then cured at 25-75 deg.c for 1-2 days before flow casting or spinning; the flow cast or extruded filming liquid is pre-evaporated in the air for 0-120 s before curing in solidification bath in pH 0.4-4 or pH 10-13; and the cured film is further soaked in the solidification bath for 5-25 min and soaked in pure water for 1-2 days. The reinforced hybrid organic-inorganic film has simplified preparation process and high mechanical strength.
Description
Technical field
The preparation method of the organic-inorganic hybridized film of enhancement mode belongs to a kind of preparation field of organic-inorganic diffusion barrier.
Background technology
In recent years, membrane technology was applied to urban water supply and sewage disposal gradually, but water treatment water penetration, resistance tocrocking and the intensity of film are had higher requirement, traditional milipore filter can't satisfy the needs of water treatment large-scale application.So develop some novel membrane materials gradually, mainly contain Kynoar (PVDF), polyvinyl chloride (PVC), polysulfones (PSF), polyether sulfone (PES), polyacrylonitrile (PAN), polyimides (PI) etc.Because feedwater, the pollutant quality is big in middle water, the especially sewage, the kind complexity, and The decline of membrane flux is serious, need carry out physics continually and clean under high strength, to keep its water flux.But there is the problem that intensity is low and the life-span is short in present normally used film, and wherein the film strength problem is particularly outstanding.
For the organic film of macromolecule, advantage such as pliability is good, simple for production because it has, the loading density of film is big, filming performance is excellent, permeability and selectivity are all high, wide in variety, thus obtain large-scale application.But organic film mechanical strength is bad, scarcely high temperature resistant and organic solvent, and corrosion resistance is poor, and easily stops up, easy cleaning not, thereby be restricted in the application in some field.
Compare with organic film, inoranic membrane has excellent mechanical property, as high surface hardness, modulus and intensity.Chemically-resistant and bioerosion, high temperature resistant, long service life, and pore-size distribution is narrow, and the separative efficiency height is easy to sterilization and cleans, so in film separation process and film coupling process good prospects for application is arranged.But the inoranic membrane selectivity is relatively poor, and the fragility of membrane material and low processing integrated level (effective filling area of film in the unit volume), high equipment investment cost are restricted its application.
Therefore there is the researcher to carry out the compound organic-inorganic film made from inorganic and organic material, not only can take into account organic film and inoranic membrane advantage separately, remedy the defective of single membrane material, but also can develop the combination property that single membrane material did not originally have, enlarge range of application, satisfy specific application requirements.
The preparation method of hybrid inorganic-organic diffusion barrier mainly contains following several in the various documents of present stage:
1. in the casting solution of organic film, directly add inorganic particle
Instantiation can be with reference to following document: Peng Yuelian, Liu Yan, money English. nanometer SiO
2Influence research to polyvinylidene fluoride (PVDF) ultrafiltration membrane. membrane science and technology.2006.26 (1); Jiang Yunpeng, Wang Rongshu. nanometer SiO
2The preparation of/PVA composite hyperfiltration membrane and performance study. polymer material science and engineering .2002.18 (5); Li Jiansheng, beam Groceries .TiO such as Wang Huiya
2The preparation of/PVDF composite hollow fiber membrane and sign. macromolecule journal .2004; Beam Groceries, Li Jiansheng, Sun Xiuyun etc. nanometer γ-Al
2O
3The structural research of/PVDF hollow-fibre membrane. water technology .2004.30 (4); Xu Dongmei, Zhang Keda, Fan Zhihong etc. nanometer SiO2 modified polyvinylalcohol infiltrating and vaporizing membrane. chemical science and technology .2003.11 (2); Bottino A, Capannelli G, D ' Asti A, et al.Preparation andproperties lf novel organic-inorganic porous membranes.Separation purificationtechnology.2001.22-23:269-275; Bottino A, Capannelli G, Comite A.Preparationand characterization of novel porous PVDF-ZrO
2Composite membranes.Desalination.2002.146:35-40 etc.Studies show that more than the hybrid inorganic-organic diffusion barrier that this kind method makes is having greatly improved aspect ultrafiltration performance and the hydrophilicity, and effect is also not obvious on the mechanical property that improves film.
In terms of overall, this kind method is simple to operate, can use with traditional Polymer Processing moulding process, mechanical bond, good industrialization production feasibility, be similar to the blending and modifying of polymer, be the simplest method of preparation organic-inorganic nanocomposite, be suitable for the inorganic nano-particle of various forms.But defective is: make inorganic nano-particle even with nanoscopic level dispersion, have certain difficulty, will carry out surface treatment to particle usually.And the new chemical bond of difficult formation between inorganic particle and the organic polymer, just be dispersed in the network of organic polymer effect and not obvious on the mechanical property that improves film simply.
2. in the casting solution of organic film, directly add inorganic sol
Instantiation can be with reference to following document: Yu Kun, in the advanced person. nanometer SiO
2-Al
2O
3The preparation of hybrid film of polyimide and sign. Shandong Technology Univ's journal (natural science edition) .2006.20 (4); Wu Daqing. the preparation and the sign of inorganic doping modified polyimide film. material science and technology .2006.14 (4); Dou Yan, Cui Peng .TiO
2The preparation of nano thin-film and performance study. HeFei University of Technology's journal (natural section version) .2006.29 (1); Dong Tiequan, Zhang Mingyan, Ceng Shujin. the preparation and the performance evaluation of polyimide/silicon dioxide/nano titania hybridized film. insulating materials .2005.7; SCHULER T, KRAKEWSHI T, GROBELSEK I, etal.Influence of Structure Zone Model Parameters on the Electrical Properties ofZnO:Al Sol-gel Coatings[J] .Thin Solid Films, 2006,502:67-71; WANGMR, WANGJ, CHEN W, et al.Effect of Preheating and Annealing Temperatures onQuality Characteristicsof ZnO Thin FilmPrepared by Sol-gel Method[J] .Materials Chemistry andPhysics, 2006.97:219-225; Wei Ming, Tan accounts for a flat iron plate for making cakes. preparation, structure and the performance characterization of shitosan/silica nanometer composite membrane. and Wuhan University of Technology's journal (information and management engineering version) .2006.28 (1) etc.Studies show that hybrid inorganic-organic diffusion barrier that this kind method makes focuses mostly at hydrophily, anti-fouling performance, high temperature oxidation resisting, corrosion resistance and film self cleaning capacity that improves film etc.In as above report, except the mechanical property of shitosan/silica nanometer composite membrane made moderate progress, other film strength was not seen improvement.In addition, this kind method operation more complicated, and also have that a lot of problems such as film poor adhesive force, film thickness on body are too thin, compactness is poor, difficult grasp etc. of easy to crack, technological parameter wait further to research and solve.
3. in the casting solution of organic film, add the presoma of inorganic particulate and the catalyst of hydrolytic polymerization thereof
Concrete case study: S.P.Nunesa, K.V.Peinemanna, K.Ohlrogge, what et al.Membranes of poly (ether imide) and nanodispersed silica.Journal of MembraneScience 157 (1999) 219-226. the researches were different with above-mentioned other researchs is that the author is directly with SiO
2The presoma ethyl orthosilicate add in the casting solution of PEI, and in casting solution, add the catalyst hydrochloric acid of teos hydrolysis polymerization, hydrolytic-polymeric reaction has taken place in ethyl orthosilicate in the process of casting solution slaking, generates SiO
2, to realize that inorganic polymer and organic polymer are in the molecule level mixture.The author has studied and added ethyl orthosilicate and the vitrification point (Tg) of hydrochloric acid caudacoria and the variation of structure thereof in casting solution, and the result shows: along with the adding of inorganic component, the form of film becomes spongelike structure from finger piece; The film that inorganic component content is high has better stability under the effect of pressure.Other report that utilizes this method to make organic-inorganic hybridized film is not at present also found.
The shortcoming of this kind method: add the dissolving that catalyst (hydrochloric acid) is unfavorable for organic polymer in the casting solution, defective, poor repeatability appear in the final film that forms easily; Hydrolysis and polymerization take place in inorganic precursor in the process of casting solution slaking, be difficult to the molecular weight of control inorganic polymer, form large-sized inorganic spheric granules easily, are difficult to realize the molecule level mixture between inorganic phase and the organic facies.
Summary of the invention
The present invention improves method 3, promptly only in casting solution, add the presoma of inorganic particulate, do not add the catalyst of presoma hydrolytic polymerization, casting solution through after the overcuring in the catalyst of inorganic precursor hydrolytic polymerization film forming, the hydrolysis and the polymerization of inorganic precursor taking place in the organic film forming process of macromolecule simultaneously, generate linear inorganic polymer, and twines with organic polymer, form interpenetrating networks, the final organic and inorganic diffusion barrier that strengthens that forms.The film that this method obtains has better homogeneity, be not separated, and insoluble polymer also can participate in the organic and inorganic network.
The invention provides that a kind of technology is simple, cost is low and having selected has the inorganic precursor of fine compatibility to prepare dull and stereotyped hybridized film of enhancement mode organic-inorganic or doughnut hybridized film as additive with the casting solution solvent.
The technical solution adopted in the present invention is:
Utilize SiO
2, TiO
2, Al
2O
3, ZrO
2, SnO
2Or the presoma of ZnO etc. characteristics of hydrolysis-polymerization fast under acidity or alkali condition, directly can pass through inorganic precursor ethyl orthosilicate (TEOS), butyl titanate (TBT), the aluminium isopropoxide (Al (OCHC of interpolation above-mentioned substance in the organic polymer casting solution of L-S inversion of phases legal system film to Kynoar (PVDF), polyvinyl chloride (PVC), polysulfones (PSF), polyether sulfone (PES), polyacrylonitrile (PAN), polyimides (PI) etc.
2O
5CH
3)
3), zirconium oxychloride (ZrOCl
28H
2O) or zinc acetate (Zn (CH
3COO)
22H
2O), anhydrous stannic chloride (SnCl
4) add certain quantity of additive polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), anhydrous Lithium chloride (LiCl) etc. simultaneously and with acid (pH=0.4-4) or alkali (pH=10-13) solution as coagulating bath, control conditions such as certain prevapourising time, casting solution temperature, coagulation bath composition, have machine-inorganic hybrid membrane with L-S phase inversion or spinning method.
The preparation method of above-mentioned high strength hybridized film is characterized in that it may further comprise the steps:
1) solvent and inorganic precursor are mixed, add organic polymer and additive again and obtain the blend casting solution, wherein the quality percentage composition of above-mentioned substance in casting solution is respectively: organic polymer 10%-20%, additive 0-10%, solvent 55-80%, inorganic precursor 0-24%; Described organic polymer is: Kynoar (PVDF), polyvinyl chloride (PVC), polysulfones (PSF), polyether sulfone (PES), polyacrylonitrile (PAN), polyimides (PI);
Described additive is: polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), anhydrous Lithium chloride (LiCl);
Described solvent is: dimethylacetylamide (DMAc), dimethyl formamide (DMF), N-methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO);
Described inorganic precursor is: ethyl orthosilicate (TEOS), butyl titanate (TBT), aluminium isopropoxide (Al (OCHC
2O
5CH
3)
3), zirconium oxychloride (ZrOCl
28H
2O) or zinc acetate (Zn (CH
3COO)
22H
2O), anhydrous stannic chloride (SnCl
4);
2) with above-mentioned casting solution curtain coating or spinning film forming after slaking 1-2 days in 25 ℃-75 ℃ baking oven;
3) above-mentioned film is put into the coagulating bath of pH=0.4-4 or pH=10-13 behind the prevapourising 0-120s in air, solidified the back and in coagulating bath, soaked 5-25 minute, in pure water, soaked 1-2 days again, promptly obtain high strength hybridized film of the present invention.
In the casting solution component of the present invention: organic polymer can be that a kind of in the above-mentioned high polymer also can be the mixture of several high polymers; Inorganic precursor can be that a kind of of above-mentioned inorganic precursor also can be the mixture of several inorganic precursors.
Kynoar of the present invention (PVDF), polyvinyl chloride (PVC), polysulfones (PSF), polyether sulfone (PES), polyacrylonitrile (PAN), polyimides organic polymers such as (PI) have good solubility, and they are soluble in dimethylacetylamide (DMAc), dimethyl formamide (DMF), N-methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) organic solvents such as (DMSO); Above organic polymer of while is also nontoxic, nothing is smelt, and has good insulation performance, film forming and resistance property etc.
Additive inorganic precursor ethyl orthosilicate of the present invention (TEOS), butyl titanate (TBT), aluminium isopropoxide (Al (OCHC
2O
5CH
3)
3), zirconium oxychloride (ZrOCl
28H
2O), anhydrous stannic chloride (SnCl
4) or zinc acetate (Zn (CH
3COO)
22H
2O) etc. with the solvent dimethylacetylamide (DMAc) of this experiment, dimethyl formamide (DMF), N-methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO) etc. has good intersolubility, and do not influence organic polymer Kynoar (PVDF) during smaller or equal to 24wt% at its addition, polyvinyl chloride (PVC), polysulfones (PSF), polyether sulfone (PES), polyacrylonitrile (PAN), polyimides (PI) etc. and additive polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), the dissolubility of anhydrous Lithium chloride (LiCl) etc., can form the casting solution of homogeneous transparent, guarantee the superperformance of film.
Film-forming method of the present invention is simple, and promptly Chang Yong L-S phase inversion prepares the technical process that flat sheet membrane or spin processes prepare hollow-fibre membrane.
The present invention has exempted in original technology compared with the prior art to the particle diameter and the inhomogeneity requirement for height thereof of inorganic particulate, has simplified experimentation.Directly in casting solution, add inorganic precursor and be relatively easy to the organic-inorganic hybridized film of the type of being enhanced.And the hybridized film of gained of the present invention is guaranteeing to obtain the higher hydridization diffusion barrier of intensity under the identical ultrafiltration performance condition.For film is providing more wide application prospect aspect sewage disposal and the membrane bioreactor etc.
The specific embodiment
Embodiment 1 does not contain the preparation of Kynoar (PVDF) hybridized film of additive
Casting solution is made up of PVDF, DMAC, TEOS, and the quality percentage composition is respectively 15%, 79% and 6%.
At first PVDF, TEOS are mixed with DMAC stir a period of time after, the casting solution that obtains clarifying, afterwards in 45 ℃ of following slakings 2 days, curtain coating after the deaeration, the preparation liquid of curtain coating volatilize in air enters the middle film-forming of hydrochloric acid-aqueous solution (pH=1) behind the 15s.This film continues to soak in coagulating bath to take out after about 5 minutes and immersed in the deionized water 1 day.
Utilize GT-TS-2000 type stretching strength determination instrument respectively to the maximum intensity and the elastic modelling quantity of the pvdf membrane that do not add TEOS and the pvdf membrane that contains TEOS at ambient temperature.The maximum intensity that records the film that contains TEOS is 7.92MPa, and elastic modelling quantity is 212.06Map, increases about 2 times than the film that does not add ethyl orthosilicate.
Embodiment 2 contains the preparation of Kynoar (PVDF) hybridized film of additive (PVP and LiCl)
Casting solution is made up of PVDF, PVP, LiCl, DMAC, TEOS, and the quality percentage composition is respectively 15%, 4%, 3%, 64% and 14%.
At first PVDF, PVP, anhydrous LiCl, TEOS are mixed stirring a period of time with DMAC after, the casting solution that obtains clarifying, afterwards in 35 ℃ of following slakings 1 day, curtain coating after the deaeration, the preparation liquid of curtain coating enters film-forming in hydrochloric acid-aqueous solution (pH=1) behind air evaporation 30s, this film continues to soak in coagulating bath to take out after about 25 minutes and immersed in the deionized water 1 day.
Utilize GT-TS-2000 type stretching strength determination instrument to test maximum intensity and the elastic modelling quantity that does not add the pvdf membrane of TEOS and contain the pvdf membrane of TEOS respectively under the room temperature.The maximum intensity that records the film that contains TEOS is 2.44MPa, and elastic modelling quantity is 18.29MPa, is not add more than 3 times of TEOS.
Embodiment 3 contains the preparation of Kynoar (PVDF) hybridized film of additive (PVP and LiCl)
Casting solution is made up of PVDF, PVP, LiCl, DMF, TEOS, and the quality percentage composition is respectively 14%, 2%, 4%, 64% and 16%.
After at first quantitative PVDF, PVP, LiCl, DMF, TEOS being mixed stirring a period of time, the casting solution that obtains clarifying is afterwards in 55 ℃ of following slakings 2 days, carry out curtain coating after the deaeration, the preparation liquid of curtain coating at air evaporation 30s, is entered in hydrochloric acid-aqueous solution (pH=1) film-forming again.This film continues to soak in coagulating bath to take out after about 25 minutes and immersed in the deionized water 2 days.
Utilize GT-TS-2000 type stretching strength determination instrument to test maximum intensity and the elastic modelling quantity that does not add the pvdf membrane of TEOS and contain the pvdf membrane of TEOS respectively under the room temperature.The maximum intensity that records the film that contains TEOS is 1.83MPa, and elastic modelling quantity is 27.1MPa, is not add more than 2 times of TEOS.
Embodiment 4 contains the preparation of Kynoar (PVDF) hybridized film of additive (PVP and LiCl)
Casting solution is made up of PVDF, PVP, LiCl, DMAC, TEOS, and the quality percentage composition is respectively 16%, 3%, 2%, 59% and 20%.
After at first PVDF, PVP, LiCl, DMAC, TEOS being mixed stirring a period of time, the casting solution that obtains clarifying is afterwards in 45 ℃ of following slakings 2 days, carry out spinning after the deaeration, the preparation liquid of extruding enters in hydrochloric acid-aqueous solution (pH=1) film-forming afterwards at air evaporation 30s.This hollow-fibre membrane continues to soak in coagulating bath to take out after about 25 minutes and immersed in the deionized water 2 days.
Utilize GT-TS-2000 type stretching strength determination instrument to test maximum intensity and the elastic modelling quantity that does not add the pvdf membrane of TEOS and contain the pvdf membrane of TEOS respectively under the room temperature.The maximum intensity that records the film that contains TEOS is 2.28MPa, and elastic modelling quantity is 16.4MPa.Be not add more than 3 times of TEOS.
The preparation of embodiment 5 enhancement mode polyvinyl chloride (PVC) hybridized film
Casting solution is made up of PVC, PVP, NMP, TBT, and the quality percentage composition is respectively 15%, 5%, 70% and 20%.
After at first PVC, PVP, NMP, TBT being mixed stirring a period of time, the casting solution that obtains clarifying is afterwards in 60 ℃ of following slakings 1 day, carry out curtain coating after the deaeration, the preparation liquid of curtain coating at air evaporation 60s, is entered in nitric acid-aqueous solution (pH=2) film-forming afterwards.This film continues to soak in coagulating bath to take out after about 15 minutes and immersed in the deionized water 2 days.
The maximum intensity and the elastic modelling quantity that utilize GT-TS-2000 type stretching strength determination instrument to test the PVC film that does not add TBT respectively and contained the PVC hybridized film of TBT under the room temperature.The maximum intensity that records the film that contains TBT is 1.76MPa, and elastic modelling quantity is 13.68MPa.Be not add more than 1 times of TBT.
The preparation of embodiment 6 enhancement mode polyvinyl chloride (PVC) hybridized film
Casting solution is made up of PVC, PVP, DMAC, TBT, and the quality percentage composition is respectively 20%, 3%, 63% and 14%.
After at first quantitative PVC, PVP, DMAC, TBT being mixed stirring a period of time, the casting solution that obtains clarifying is afterwards in 60 ℃ of following slakings 1 day, carry out spinning after the deaeration, the preparation liquid of extruding enters in nitric acid-aqueous solution (pH=2) film-forming afterwards at air evaporation 60s.This hollow-fibre membrane continues to soak in coagulating bath to take out after about 15 minutes and immersed in the deionized water 1 day.
The maximum intensity and the elastic modelling quantity that utilize GT-TS-2000 type stretching strength determination instrument to test the PVC film that does not add TBT respectively and contained the PVC hybridized film of TBT under the room temperature.The maximum intensity that records the film that contains TBT is 2.28MPa, and elastic modelling quantity is 16.75MPa, is not add more than 2 times of TBT.
The preparation of embodiment 7 enhancement mode polyether sulfone (PES) hybridized film
Casting solution is by PES, PEG, DMSO, ZrOCl
28H
2O forms, and the quality percentage composition is respectively 20%, 10%, 54% and 16%.
At first with quantitative PES, PEG, DMSO, ZrOCl
28H
2After O mix to stir a period of time, the casting solution that obtains clarifying in 25 ℃ of following slakings 1 day, carried out curtain coating afterwards after the deaeration, and the preparation liquid of curtain coating at air evaporation 90s, is entered in nitric acid-aqueous solution (pH=0.4) film-forming afterwards.This film continues to soak in coagulating bath to take out after about 20 minutes and immersed in the deionized water 1 day.
Utilize GT-TS-2000 type stretching strength determination instrument to test respectively under the room temperature and do not add ZrOCl
28H
2The PES film of O and the PESZrOCl that contains
28H
2The maximum intensity and the elastic modelling quantity of O hybridized film.Record and contain ZrOCl
28H
2The maximum intensity of the film of O is 1.96MPa, and elastic modelling quantity is 13.58MPa, is not add ZrOCl
28H
2About 2 times of O.
The preparation of embodiment 8 enhancement mode polyether sulfone (PES) hybridized film
Casting solution is by PES, PEG, DMSO, ZrOCl
28H
2O forms, and the quality percentage composition is respectively 15%, 6%, 55% and 24%.
At first with quantitative PES, PEG, DMSO, ZrOCl
28H
2After O mixed stirring a period of time, the casting solution that obtains clarifying in 60 ℃ of following slakings 1 day, carried out spinning afterwards after the deaeration, and the preparation liquid of extruding enters film-forming in nitric acid-aqueous solution (pH=0.4) after air evaporation 90s.This hollow-fibre membrane continues to take out after coagulating bath is soaked about 20 minutes and immersed in the deionized water 2 days.
Utilize GT-TS-2000 type stretching strength determination instrument to test respectively under the room temperature and do not add ZrOCl
28H
2The PES film of O and contain ZrOCl
28H
2The maximum intensity and the elastic modelling quantity of the PES hybridized film of O.Record and contain ZrOCl
28H
2The maximum intensity of the film of O is 1.66MPa, and elastic modelling quantity is 12.08MPa, is not add ZrOCl
28H
2More than 1.5 times of O.
The preparation of embodiment 9 enhancement mode polysulfones (PSF) hybridized film
Casting solution is by PSF, PVP, DMF, Al (OCHC
2O
5CH
3)
3Form, the quality percentage composition is respectively 17%, 4%, 63% and 16%.
At first with quantitative PSF, PVP, DMF, Al (OCHC
2O
5CH
3)
3After mixing stirring a period of time, the casting solution that obtains clarifying, afterwards in 75 ℃ of following slakings 2 days, spinning after the deaeration, the preparation liquid of extruding will enter film-forming in the ammonia spirit (pH=11) behind air evaporation 120s.This hollow-fibre membrane continues to take out after coagulating bath is soaked about 20 minutes and immersed in the deionized water 2 days.
After treating that film is peeled off from glass plate fully, soak after about 15 minutes film taken out from coagulating bath and immersed in the deionized water 2 days.
Utilize GT-TS-2000 type stretching strength determination instrument to test respectively under the room temperature and do not add Al (OCHC
2O
5CH
3)
3The PSF film and contain Al (OCHC
2O
5CH
3)
3The maximum intensity and the elastic modelling quantity of PSF hybridized film.Record and contain Al (OCHC
2O
5CH
3)
3The maximum intensity of film be 2.15MPa, elastic modelling quantity is 21.36MPa, is not add Al (OCHC
2O
5CH
3)
3About 2 times.
The preparation of embodiment 10 enhancement mode polysulfones (PSF) hybridized film
Casting solution is by PSF, PVP, NMP, Al (OCHC
2O
5CH
3)
3Form, the quality percentage composition is respectively 12%, 6%, 74% and 8%.
At first with PSF, PVP, NMP, Al (OCHC
2O
5CH
3)
3After mixing stirring a period of time, the casting solution that obtains clarifying, afterwards in 35 ℃ of following slakings 1 day, curtain coating after the deaeration, the preparation liquid of curtain coating enters film-forming in hydrochloric acid-aqueous solution (pH=4) behind air evaporation 80s.This film continued to soak in coagulating bath to take out after about 25 minutes immersed in the deionized water 1 day.
Utilize GT-TS-2000 type stretching strength determination instrument to test respectively under the room temperature and do not add Al (OCHC
2O
5CH
3)
3The PSF film and contain Al (OCHC
2O
5CH
3)
3The maximum intensity and the elastic modelling quantity of PSF hybridized film.Record and contain Al (OCHC
2O
5CH
3)
3The maximum intensity of film be 1.13MPa, elastic modelling quantity is 6.36MPa, is not add Al (OCHC
2O
5CH
3)
3About 0.5 times.
The preparation of embodiment 11 enhancement mode polysulfones (PSF) hybridized film
Casting solution is made up of PSF, PVP, DMAC, TEOS, and the quality percentage composition is respectively 15%, 5%, 66% and 14%.
After at first quantitative PSF, PVP, DMAC, TEOS being mixed stirring a period of time, the casting solution that obtains clarifying, afterwards in 35 ℃ of following slakings 1 day, curtain coating after the deaeration, the preparation liquid of curtain coating enters film-forming in the ammonia spirit (pH=11) behind air evaporation 120s.This film soaks after about 15 minutes to take out in coagulating bath and immersed in the deionized water 1 day.
The maximum intensity and the elastic modelling quantity that utilize GT-TS-2000 type stretching strength determination instrument to test the PSF film that does not add TEOS respectively and contained the PSF hybridized film of TEOS under the room temperature.The maximum intensity that records the film that contains TEOS is 2.63MPa, and elastic modelling quantity is 10.36MPa, is not add more than 2 times of TEOS.
The preparation of embodiment 12 enhancement mode polyacrylonitrile (PAN) hybridized film
Casting solution is by PAN, PEG, LiCl, DMAC, Zn (CH
3COO)
22H
2O forms, and the quality percentage composition is respectively 20%, 2%, 4%, 64% and 10%.
At first with quantitative PAN, PEG, LiCl, DMAC, Zn (CH
3COO)
22H
2After O mixes stirring a period of time, the casting solution that obtains clarifying, afterwards in 45 ℃ of following slakings 1 day, curtain coating after the deaeration, the preparation liquid of curtain coating enters film-forming in NaOH-aqueous solution (pH=13) behind air evaporation 60s.This film soaks after about 20 minutes to take out in coagulating bath and immersed in the deionized water 1 day.
Utilize GT-TS-2000 type stretching strength determination instrument to test respectively under the room temperature and do not add Zn (CH
3COO)
22H
2The PAN film of O and contain Zn (CH
3COO)
22H
2The maximum intensity and the elastic modelling quantity of the PAN hybridized film of O.Record and contain Zn (CH
3COO)
22H
2The maximum intensity of the film of O is 1.38MPa, and elastic modelling quantity is 9.36MPa, is not add Zn (CH
3COO)
22H
2More than 1 times of O.
The preparation of embodiment 13 enhancement mode polyacrylonitrile (PAN) hybridized film
Casting solution is by PAN, PEG, LiCl, DMF, Zn (CH
3COO)
22H
2O forms, and the quality percentage composition is respectively 18%, 6%, 1.5%, 60.5% and 14%.
At first with quantitative PAN, PEG, LiCl, DMF, Zn (CH
3COO)
22H
2After O mixes stirring a period of time, the casting solution that obtains clarifying, afterwards in 50 ℃ of following slakings 1 day, spinning after the deaeration, the preparation liquid of extruding enters film-forming in NaOH-aqueous solution (pH=13) behind air evaporation 60s.This film soaks after about 20 minutes to take out in coagulating bath and immersed in the deionized water 1 day.
Utilize GT-TS-2000 type stretching strength determination instrument to test respectively under the room temperature and do not add Zn (CH
3COO)
22H
2The PAN film of O and contain Zn (CH
3COO)
22H
2The maximum intensity and the elastic modelling quantity of the PAN hybridized film of O.Record and contain Zn (CH
3COO)
22H
2The maximum intensity of the film of O is 2.38MPa, and elastic modelling quantity is 30.86MPa, is not add Zn (CH
3COO)
22H
2More than 2 times of O.
The preparation of embodiment 14 enhancement mode polyacrylonitrile (PAN) hybridized film
Casting solution is by PAN, PEG, LiCl, DMAC, Zn (CH
3COO)
22H
2O forms, and the quality percentage composition is respectively 15%, 2%, 6%, 62% and 15%.
At first with quantitative PAN, PEG, LiCl, DMAC, Zn (CH
3COO)
22H
2After O mixes stirring a period of time, the casting solution that obtains clarifying, afterwards in 45 ℃ of following slakings 1 day, curtain coating after the deaeration, the preparation liquid of curtain coating enters film-forming in nitric acid-aqueous solution (pH=3) behind air evaporation 60s.This film soaks after about 25 minutes to take out in coagulating bath and immersed in the deionized water 2 days.
Utilize GT-TS-2000 type stretching strength determination instrument to test respectively under the room temperature and do not add Zn (CH
3COO)
22H
2The PAN film of O and contain Zn (CH
3COO)
22H
2The maximum intensity and the elastic modelling quantity of the PAN hybridized film of O.Record and contain Zn (CH
3COO)
22H
2The maximum intensity of the film of O is 2.18MPa, and elastic modelling quantity is 20.86MPa, is not add Zn (CH
3COO)
22H
2About 2 times of O.
The preparation of embodiment 15 enhancement mode polyacrylonitrile (PI) hybridized film
Casting solution is by PI, PEG, DMAC, SnCl
4Form, the quality percentage composition is respectively 15%, 6%, 65% and 14%.
At first with quantitative PI, PEG, DMAC, SnCl
4After mixing stirring a period of time, the casting solution that obtains clarifying, afterwards in 45 ℃ of slakings 1 day, curtain coating after the deaeration, the preparation liquid of curtain coating enters film-forming in nitric acid-aqueous solution (pH=1) behind air evaporation 80s.This film soaks after about 25 minutes to take out in coagulating bath and immersed in the deionized water 2 days.
Utilize GT-TS-2000 type stretching strength determination instrument to test respectively under the room temperature and do not add SnCl
4The PI film and contain SnCl
4The maximum intensity and the elastic modelling quantity of PI hybridized film.Record and contain SnCl
4The maximum intensity of film be 3.18MPa, elastic modelling quantity is 24.26MPa, is not add SnCl
4About 3 times.
Claims (1)
1, the preparation method of the organic-inorganic hybridized film of a kind of enhancement mode is characterized in that it may further comprise the steps:
1) organic polymer, additive, solvent and inorganic precursor are mixed, obtain the blend casting solution, wherein the quality percentage composition of above-mentioned substance in casting solution is respectively: organic polymer 10%-20%, additive 0-10%, solvent 55-80%, inorganic precursor 0-24%;
Described organic polymer is: Kynoar, polyvinyl chloride, polysulfones, polyether sulfone, polyacrylonitrile, polyimides;
Described additive is: polyvinylpyrrolidone, polyethylene glycol, anhydrous Lithium chloride;
Described solvent is: dimethylacetylamide, dimethyl formamide, N-methyl pyrrolidone, dimethyl sulfoxide (DMSO);
Described inorganic precursor is: ethyl orthosilicate, butyl titanate, aluminium isopropoxide, zirconium oxychloride, anhydrous stannic chloride or zinc acetate;
2) with curtain coating or the spinning after 25 ℃ of-75 ℃ of following slaking 1-2 days of above-mentioned casting solution;
3) the film liquid of above-mentioned curtain coating or spinning is put into the coagulating bath of pH=0.4-4 or pH=10-13 behind the prevapourising 0-120s in air, film-forming continues to soak 5-25 minute in coagulating bath, soaks 1-2 days in pure water again.
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| WO2024140892A1 (en) * | 2022-12-28 | 2024-07-04 | 嘉庚创新实验室 | Composite diaphragm for hydrogen production by alkaline electrolyzed water, and preparation method for composite diaphragm |
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| CN100463712C (en) | 2009-02-25 |
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