CN1730141A - Process for preparing co-mixed polyethersulfone platform complex film - Google Patents
Process for preparing co-mixed polyethersulfone platform complex film Download PDFInfo
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- CN1730141A CN1730141A CN 200510060289 CN200510060289A CN1730141A CN 1730141 A CN1730141 A CN 1730141A CN 200510060289 CN200510060289 CN 200510060289 CN 200510060289 A CN200510060289 A CN 200510060289A CN 1730141 A CN1730141 A CN 1730141A
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Abstract
The invention discloses a method for preparing slab-shaped complex film made by blending polyethersulfone. Various film-forming agents according to certain proportion are made by blending polymer (polyethersulfone and sulfonated polyethersulfone), additive, non-solvent and organic solvent. Complex film is prepared on traditional shearing machine via pouring film-forming agents into loading chute, entering knife-edge groove, covering solution on supporting layer and dipping it into coagulating bath. The invention is characterized in that mainly via adjusting composition of film-forming agents, it prepares slab-shaped complex film with high intensity, high water flux and good hydrophilicity.
Description
Technical field
The invention belongs to the membrane separation technique field, the preparation method of the co-mixed polyethersulfone platform complex film of particularly a kind of high flux, high mechanical properties and excellent hydrophilic.
Background technology
The engineering plastics of a kind of superior performance of polyether sulfone (PES), its vitrification point have the performance of good especially heat-resisting water and high-temperature resistant water steam up to 225 ℃.It is in 130～140 ℃ hot water and water vapour, and structure can not be damaged, and just when temperature exceeds more than 150 ℃, just can produce deformation and performance degradation.PES has excellent mechanical property, and excellent hear resistance, alkaline-resisting, compression resistance, corrosion-resistant and superior performances such as blood compatibility are that a kind of good microporous barrier prepares material.This material can be dissolved in dimethyl sulfoxide (DMSO), N, dinethylformamide, N, and N-dimethylacetylamide, N-methyl pyrrolidone etc. being configured to polymer solution in the various polarity solvent, are fit to immersion precipitation inversion of phases legal system film very much.
In immersion precipitation phase inversion film-forming process, polymer solution elder generation hydrostomia is extruded on reinforcing material or from spinning nozzle, then immerse rapidly in the non-solvent bath, coagulating bath is immersed in the solvent diffusion, and non-solvent is diffused in the film that spreads to, through after a while, exchange between solvent and the non-solvent acquires a certain degree, polymer solution becomes thermodynamic instability, liquid-liquid phase separation or liquid one solid phase that polymer solution takes place are separated, become two-phase: polymer rich mutually and polymer stingy, polymer rich after phase-splitting the main body of just curing formation film soon, stingyly then form so-called hole.
The principal element that influences microporous membrane structure and performance has the selecting for use of polymer concentration, solvent and non-solvent, additive component and concentration, coagulating bath composition and temperature and post processing.In order to obtain the PES microporous barrier of high flux and porous surface, the preparation and the performance of PES microporous barrier many researchs have been carried out.For example, add certain amount of solvent in coagulating bath, this prevents the formation of low percent opening film surface cortex mainly by reducing the chemical potential difference of preparation liquid and coagulation bath.Adding certain quantity of additive liquid in preparation liquid is the method for a kind of simple and effective raising membrane aperture and flux, and employed additive mainly contains water soluble polymer polyvinylpyrrolidone and polyethylene glycol, inorganic salts and little molecular solvent etc.Film is carried out the high-throughout film that certain post-processing also can obtain porous.As the nascent state film is soaked stagnate with the stronger solvent of membrane interaction in after a period of time, immerse again in the non-solvent after making the abundant swelling of film, the film top layer that obtains is more loose, flux is bigger; Also have the film that will make employing certain density hypochlorite handle, the original film of the flux ratio of the film that obtains at last can be big 3～4 times.
For homogeneous PES film, breadboard research can obtain the PES film of high flux porous, generates yet these technologies are used for industry, and cost will be very high, and the porous of film has also caused film strength lower.In fact, thickness also is a factor that influences membrane structure and performance, and film is thin more, and the film mesopore is many more, and water flux is also big more, but for homogeneous membrane, if film is too thin, film will not have intensity so.Therefore the composite membrane that has supporting layer to exist can address this problem, and the existence of supporting layer both can provide enough intensity that the very thin thickness of the polymer film that can allow the upper strata is arranged.
Summary of the invention
The purpose of this invention is to provide a kind of high flux, high mechanical properties and excellent hydrophilic the preparation method of co-mixed polyethersulfone platform complex film.
The step of method is:
1) polyethersulfone blended thing (BPES) 10～13wt%, additive 0.1～20wt%, deionized water 1～8wt% are dissolved in the organic solvent, heating stirs, and filters, and obtains preparation liquid after the vacuum defoamation;
2) be that 26～28 ℃ of preparation liquids are coated on the supporter of nonwoven by knifing machine with temperature, scraping film thickness is 150～200 μ m, and the cloth speed of walking of supporting layer is 1.3～1.5m/min, and the sky time of exposing to the sun is 5s;
3) supporter that will be coated with preparation liquid immerses and to solidify in the bath water, forms microporous compound film, and coagulation bath temperature is 26～28 ℃;
4) microporous compound film was soaked in deionized water 5～7 days, then microporous compound film is dipped in the glycerine water solution of 15～20% (v/v) and carries out hydrophilicity-imparting treatment, the processing time is 20～24h;
5) microporous compound film is taken out natural airing from glycerine water solution.
Polyethersulfone blended thing is meant the blend of polyether sulfone (PES) and sulfonated polyether sulfone (SPES), and the mass ratio of polyether sulfone and sulfonated polyether sulfone is 100/0～70/30 in the preparation liquid.Organic solvent is N, N-dimethylacetylamide, N, dinethylformamide, N-methyl pyrrolidone or dimethyl sulfoxide (DMSO).Additive is polyvinylpyrrolidone (PVP) or nano titanium oxide (TiO
2) in one or both.PVP is PVP (K30), and molecular weight is 30,000, and addition is 1～20wt%.Nano-TiO
2Be Detitanium-ore-type, addition is 0.1～0.5wt%.Nonwoven is a polyester non-woven fabric, and thickness is 115～125 μ m.
Advantage of the present invention is:
1) simple, the serialization of preparation process, good reproducibility, easily industrialization;
2) coagulating bath consist of common non-solvent pure water, the temperature of preparation liquid, coagulating bath is about 28 ℃, easy control of temperature has been saved the needed energy consumption of high temperature coagulating bath; Significantly reduced production cost;
3) existence of supporting layer, make the compound film strength of gained blend polyethersulfone improve greatly, hot strength is 29.68Mpa, elongation at break is 32.53%, the hot strength of PES homogeneous membrane has only 2.21MPa, elongation at break is 10.34%, and the hot strength of composite membrane is 13.43 times of homogeneous membrane hot strength, and elongation at break is 3.15 times of homogeneous membrane;
4) supporting layer makes the top layer polymer film can apply extremely thinly, at 30～55 mu m ranges, because supporting layer can not cause resistance to filter process in microfiltration applications, therefore, this blend polyethersulfone composite membrane is much smaller to the PES homogeneous flat sheet membrane before the resistance ratios of filter process formation in microfiltration process.So the water flux of this composite membrane is greatly improved.
Description of drawings
Fig. 1 is a technical process schematic diagram of producing co-mixed polyethersulfone platform complex film continuously;
Fig. 2 (a) is the BPES composite membrane surface SEM photo that polymer concentration prepares during for 10wt%;
Fig. 2 (b) is the BPES composite membrane surface SEM photo that polymer concentration prepares during for 13wt%;
Fig. 3 (a) is the BPES composite membrane surface SEM photo that PVP content prepares during for 1wt%;
Fig. 3 (b) is the BPES composite membrane surface SEM photo that PVP content prepares during for 5wt%;
Fig. 3 (c) is the BPES composite membrane surface SEM photo that PVP content prepares during for 7wt%;
Fig. 3 (d) is the BPES composite membrane surface SEM photo that PVP content prepares during for 10wt%;
Fig. 3 (e) is the BPES composite membrane surface SEM photo that PVP content prepares during for 15wt%;
Fig. 3 (f) is the BPES composite membrane surface SEM photo that PVP content prepares during for 20wt%;
Fig. 4 (a) is the BPES composite membrane table SEM photo that non-aqueous solvent content prepares during for 2wt%;
Fig. 4 (b) is the BPES composite membrane table SEM photo that non-aqueous solvent content prepares during for 5wt%;
Fig. 4 (c) is the BPES composite membrane table SEM photo that non-aqueous solvent content prepares during for 8wt%;
Fig. 5 (a) is a nano-TiO
2BPES composite membrane surface SEM photo when content is 0.2wt%;
Fig. 5 (b) is a nano-TiO
2BPES composite membrane surface SEM photo when content is 0.5wt%;
Fig. 6 is the XRD spectra of composite membrane;
BPES composite membrane surface SEM photo when Fig. 7 (a) is PES/SPES=100/0 (wt);
BPES composite membrane surface SEM photo when Fig. 7 (b) is PES/SPES=90/10 (wt);
BPES composite membrane surface SEM photo when Fig. 7 (c) is PES/SPES=80/20 (wt);
BPES composite membrane surface SEM photo when Fig. 7 (d) is PES/SPES=70/30 (wt);
The specific embodiment
40～45 ℃ of abundant stirring and dissolving in flask, the time is 36～48h with a certain proportion of blend polyethersulfone (BPES), additive and solvent in the present invention.The solution of said method preparation is filtered set aside for use with Buchner funnel.Composite membrane prepares on traditional compound knifing machine.The nonwoven supporting layer walk cloth speed 1.3～1.5m/min; Scraping film thickness (thickness of liquid film) is 140～180 μ m; With temperature is in 26～28 ℃ of preparation liquid feed wells of falling the knifing machine, through measuring pump, enter in the edge of a knife groove, start, the supporting layer operation, solution is coated with to be scraped on the supporting layer, and nascent composite membrane moves 5s in air, being immersed in temperature subsequently is that polymer solution is freezing film on supporting layer in 26～28 ℃ of coagulating baths.The composite membrane of scraping was soaked in deionized water 5～7 days, make fully exchange of solvent and non-solvent (water).Then film is carried out post processing, wet film is soaked 24h in 15～20% glycerine water solution, natural then airing (Fig. 1).
PES used herein and SPES are that Changchun Jida Advanced Material Co., Ltd produces, and the PES viscosity average molecular weigh is 45000g/mol.The content of blend polyethersulfone (BPES) in preparation liquid is 10～13% (wt), when polymer concentration is lower than 10wt%, solution viscosity, the curtain coating of film forming is poor, and scrapes thin film thickness, and this all makes resulting composite membrane be easy to generate defective; When concentration was higher than 13wt%, resin content height in the preparation liquid reduced pore-foaming agent content, and these all make the gained membrane porosity reduce, and the film surface compact can not get the film of high water flux.In the present invention, increase with BPES concentration, thickness increases, and surperficial average pore size reduces, and water flux reduces gradually.According to principle of dynamics, after preparation liquid immerses coagulation bath, solvent and non-solvent will spread mutually by preparation liquid/coagulating bath interface, and cause the phase-splitting of polymer solution generation liquid liquid, increase along with polymer concentration in the preparation liquid, the liquid liquid phase-splitting of polymer-poor phase nucleation will take place in system, because formed nucleus increased during polymer was stingy, and under the promotion of concentration gradient, constantly increase, up to around rich in polymers continuous phase till gelation is solidified, the formed network structure of these nucleus is fine and close more after sloughing solvent, and the hole proportion reduces, and the porosity of film reduces; On the other hand, increase along with polymer concentration in the preparation liquid, solution viscosity also increases thereupon, non-solvent dynamics exchange process obviously slows down in solvent in the preparation liquid and the coagulating bath thereby make, the feasible delay behavior that is separated is obvious, suppress finger-like pore generation in the film, the film superficial layer of generation is finer and close, and water flux reduces.(example 1, Fig. 2).
Among the present invention, be N as the employed solvent of preparation liquid, N-dimethylacetylamide (DMAc), N-methyl pyrrolidone (NMP), N, dinethylformamide (DMF) or dimethyl sulfoxide (DMSO) (DMSO), total addition is: 67～89wt%.With them is that the water flux of the composite membrane made of solvent increases (example 2) successively.Press macromolecule similar compatibility principle, solubility parameter is close, and promptly Δ δ value is more little, and compatibility is good more, solvent DMSO, DMF, NMP, DMAc to the solvability of blend polyethersulfone are: DMAc＞NMP＞DMF＞DMSO with the compatibility of solidifying bath water is: DMSO＞DMF＞NMP＞DMAc.The solvability of solvent is strong more, and the settling velocity of film is slow more.Form finer and closely woven hole easily, so its aperture number of film that BPES-DMAc preparation liquid system forms is more, permeation rate is less.Otherwise. solvent is more little with the Δ δ value of solidifying bath water, and the BPES settling velocity is accelerated.Be tending towards forming the film of large-sized finger-like pore, then permeation rate is bigger.
Among the present invention, can add 1～20% pore additive in the preparation liquid, on the principle, additive has three aspects to the influence of membrane structure: the one, because the solvability of different additive and solvent is different, the dissolved state of polymer molecular chain in solution there is different influences; The 2nd, the adding of additive has had influence on the chemical potential of solvent, and then the mutual exchange velocity of solvent and non-solvent in the gel process of impact polymer in non-solvent, has changed the structure of film; The 3rd, water-soluble additives also very easy being dissolved in gel process solidified in the bath water, stays the space after making film solidify, and improved the degree of communication between the micropore fenestra and the porosity of film.This paper uses three class additives, and a class is hydrophilic polyvinylpyrrolidone (PVP (K30)), and a class is nano titanium oxide (TiO
2, Detitanium-ore-type), also having a class is non-aqueous solvent.At first, with the increase of PVP content, the static contact angle on composite membrane surface presents the trend that reduces, and water flux increases afterwards earlier and reduces.Analyze reason, when selecting PVP for use, because strand is longer, stronger with the effect of polymer chain, be difficult for being solidified bath water in the solidification stages of film and cement out, may part can remain in the microporous barrier after solidifying, therefore its hydrophilic effect to the BPES composite membrane is obvious, therefore with the increase of PVP content, hydrophilic effect is more obvious, and contact angle reduces (example 3).On the other hand, when PVP content from 1% to 7% increases, PVP shared volume in preparation liquid is big more, it is many more that migration is come out, final formed membrane structure is more and more loose, and macropore and finger-like pore are more and more, and the aperture of film surface holes also shows the trend of increase, the hole count of surface unit area increases, and causes the water flux of final composite membrane to increase.Yet when PVP content increased the continuation increase, water flux had reduced again mutually with average pore size.This may be because under the same situation of filming technology, the concentration of the preparation liquid of PVP high-load is bigger, in solvent and non-solvent exchange diffusion process, it is fewer that migration is come out, so PVP content shows average pore size greater than 7% telolemma and water flux all reduces (example 3, Fig. 3), so the consumption optimum value of pore additive is 6 ± 0.5wt%.
Among the present invention, the non-solvent that adds in the preparation liquid is a coagulation bath composition: deionized water.The adding of certain water gaging both can increase the film surface apertures, can reduce the use of solvent again, reduced the manufacturing cost of film.Because the existence of non-solvent, the dissolving and the swelling effect of solvent weaken, to such an extent as to the interaction between solvent and the polymer weakens, so the volume of the BPES microballoon in the preparation liquid system is just big than anhydrous system, so in film forming procedure, what the film surface apertures that the preparation liquid system obtains will be big is many.The acting on when obtaining big BPES microballoon of water in the system in addition, also make the gap on the composition of preparation liquid and coagulating bath dwindle, promptly reduced the concentration of solvent in the preparation liquid, so when being separated, in the coagulating bath in non-solvent and the preparation liquid diffusion between the solvent slow down, make the time lengthening be separated.And at the same time, because the diffusing capacity of the non-solvent that the existence of non-solvent own make to need in the preparation liquid reduces, so non-solvent is a relative process to the effect of phase separation speed.The effect of non-solvent water is to have prolonged being separated the time of surface, thereby makes the whole time lengthening that is separated, and makes the aperture on film surface become big, the structure alligatoring, the water flux of telolemma increase (example 4, Fig. 4).The addition optimum value of water is 6 ± 0.5wt% in the preparation liquid.
Another kind of additive nano-TiO
2The adding of particle, one side has improved the mechanical strength of film, is the hydrophily (example 5) in order to increase film on the other hand.This is in order to make this film can better be used for sewage treatment area.The TiO of Detitanium-ore-type
2Some degradeds biological and organic macromolecule in the energy catalysis water under the irradiation of ultraviolet light, these characteristics make this composite membrane can be applied to locating of more industrial organic wastewaters again, and do not have TiO in the technical process
2With the separation of water solution problem.TiO
2The adding of particle has improved outside the hydrophily of the mechanical strength of film and film, and the water flux of film is descended to some extent, and this is because in film forming procedure, when solvent spreads in coagulating bath with TiO
2Taken the surface of film to, however TiO
2Be not diffused in the coagulating bath fully, but stayed the surface of film, this makes the mechanical strength of film and hydrophily increase, and has stopped up the part fenestra simultaneously, make water flux descend (example 5, Fig. 5).By the sign of X-ray diffraction spectrogram, be sure oing has TiO in the residual film
2Exist (example 5, Fig. 6).
The blend of PES and hydrophily SPES is a hydrophilic method that improves the PES film, and the ratio of SPES in polymer can not be too high, though with the increase of SPES ratio, hydrophily is good more, but too a high proportion of SPES will make the water flux of film descend.This mainly is because SPES molecular weight less with respect to PES has part and diffuse in the coagulating bath as additive in film forming procedure, and the film surface holes is increased, and the SPES that stays the film surface simultaneously strengthens the film hydrophily.But when the SPES ratio was too high, polymer molecular weight reduced, solution viscosity decline, and settling velocity is accelerated, and easily forms fine and close cortex, then the water flux reduction (example 7, Fig. 7).
Among the present invention, for making in the application afterwards of prepared blend polyethersulfone micropore flat composite membrane, especially when handling the aqueous solution, so the film to gained carries out hydrophilicity-imparting treatment, soak in the glycerine water solution with composite membrane, allow and all adsorb glycerol molecule in blend polyethersulfone micropore flat composite membrane surface and the hole.
Following examples are done more detailed description to the present invention, but described embodiment is not construed as limiting the invention.
Embodiment 1
Polymer concentration is to membrane structure and Effect on Performance
With weight ratio be respectively blend polyethersulfone (PES and SPES mass ratio are 4: 1)/PVP/DMAc of 10/5/87,13/5/822 about 45 ℃ in flask abundant stirring and dissolving 36h, dissolve fully to polymer, solution keeps clarification; Above-mentioned preparation liquid is filtered with Buchner funnel, carry out vacuum defoamation, set aside for use then.Polyester non-woven fabric is installed on compound knifing machine, and the cloth speed of walking of regulating linear speed controller control nonwoven is 1.5m/s; The edge of a knife thickness of regulating between scraper and the supporting layer is 150 μ m; 26 ℃ of environment temperatures are that 26 ℃ preparation liquid is poured in the hopper with temperature, carry out knifing then, and solution is coated with to be scraped on the supporting layer, moves 5s in air, are immersed in subsequently in 28 ℃ the coagulating bath, and coagulating bath is a deionized water, the polymer solution freezing film.The composite membrane of scraping was soaked in deionized water about 7 days; Then film is carried out post processing, wet film is soaked 24h in 15% glycerine water solution, at last with film nature airing.
Carry out water flux and measure, this film at first under 0.15MPa precompressed 30 minutes basicly stable until water flux, under 0.1MPa, measure then.The configuration of surface of film by not through the dry film that glycerol liquor is handled direct gold-plated after scanning electron microscopic observation.Prepared composite membrane thickness and water flux see Table 1.The configuration of surface of various films is seen accompanying drawing 2.The homogeneous membrane that No. 1 film and phasor are formed carries out the stretching mechanical experiment, the results are shown in Table 2.
The structure and the performance of composite membrane during the different polymer concentration of table 1.
| The film numbering | Preparation liquid is formed (wt%) (BPES/PVP/DMAc) | Water flux (L/m 2h) | Thickness (μ m) |
| 1 | 10/5/85 | 875 | 164 |
| 2 | 13/5/82 | 638 | 176 |
Table 2 Mechanical test results
| Film | Hot strength MPa | Elongation at break % |
| 1 | 29.68 | 32.53 |
| Homogeneous membrane | 2.21 | 10.34 |
Solvent is to membrane structure and Effect on Performance
The blend polyethersulfone of mass ratio 10/5/85 (PES and SPES mass ratio are 4: 1)/PVP/ solvent about 45 ℃ in flask abundant stirring and dissolving 36h, dissolve fully to polymer.Solvent is respectively DMAc, NMP, DMF, DMSO.Follow-up mensuration of scraping membrane process, water flux and the sign of SEM are with embodiment 1.The thickness of prepared composite membrane, average pore size and water flux see Table 3.
The structure and the performance of flat composite membrane during the different polymer concentration of table 3.
| The film numbering | The solvent that uses | Water flux (L/m 2h) | Thickness (μ m) |
| 1 | DMAc | 875 | 164 |
| 2 | NMP | 930 | 164 |
| 3 | DMF | 1160 | 160 |
| 4 | DMSO | 1270 | 160 |
PVP content is to membrane structure and Effect on Performance
The blend polyethersulfone of mass ratio 10/1/85,10/3/87,10/5/85,10/7/83,10/10/80 (PES and SPES mass ratio are 4: 1)/PVP//DMAc about 45 ℃ in flask abundant stirring and dissolving 40h, dissolve fully to polymer.Follow-up mensuration of scraping membrane process, water flux and the sign of SEM are with embodiment 1.The measurement of contact angle is as follows, will measure contact angle with three-stage distillation water with a method of lying on contact angle instrument then less than the composite membrane of handling through glycerol liquor freeze-day with constant temperature 4 hours in 80 ℃ of baking ovens.Each sample is surveyed and is averaged for 8 times.The water flux of prepared composite membrane, thickness and contact angle see Table 4.The configuration of surface of various films is seen accompanying drawing 3.
The compound slab film properties relatively during the different PVP content of table 4.
| The film numbering | Preparation liquid is formed (wt%) (BPES/PVP/DMAc) | Water flux (L/m 2h) | Thickness (μ m) | Contact angle (°) |
| 5 | 10/1/89 | 656 | 162 | 72.8 |
| 6 | 10/3/87 | 852 | 165 | 73.9 |
| 7 | 10/7/83 | 880 | 165 | 68.5 |
| 8 | 10/10/80 | 740 | 172 | 64.9 |
| 9 | 13/15/72 | 463 | 176 | 65.3 |
| 10 | 13/20/67 | 237 | 180 | 63.9 |
Embodiment 4
Nonsolvent additive water is to membrane structure and Effect on Performance
Mass ratio is blend polyethersulfone (PES and SPES mass ratio are 4: 1)/PVP/H of 10/5/2/83,10/5/5/80,10/5/8/77
2O/DMAc about 45 ℃ in flask abundant stirring and dissolving 45h, to dissolving fully, solution keeps clarification; Follow-up mensuration of scraping membrane process, water flux and the sign of SEM are with embodiment 1, and preparation liquid and coagulation bath temperature become 26 ℃, and scraping film thickness is 180 μ m.The thickness and the water flux of prepared composite membrane see Table 5.The configuration of surface of various films is seen accompanying drawing 4.
The comparison of structure of composite membrane and performance during table 5. non-solvent water content
| The film numbering | Preparation liquid is formed (wt%) (BPES/PVP/H 2O/DMAc) | Water leads to (L/m 2h) | Thickness (μ m) |
| 11 | 10/5/2/83 | 960 | 165 |
| 12 | 10/5/5/80 | 1025 | 159 |
| 13 | 10/5/8/77 | 1244 | 154 |
Additive TiO
2To membrane structure and Effect on Performance
Mass ratio is respectively blend polyethersulfone (PES and SPES mass ratio are 4: 1)/PVP/TiO of 10/5/0.5/8/76.5,10/5/0.2/8/76.8
2/ H
2O/DMAc about 45 ℃ in flask separately abundant stirring and dissolving 48h, to dissolving fully, solution keeps clarification; Above-mentioned each preparation liquid is filtered with Buchner funnel, carry out vacuum defoamation, set aside for use then.Follow-up mensuration of scraping membrane process, water flux and the sign of SEM are with embodiment 1, and just preparation liquid and coagulation bath temperature are 26 ℃.The thickness and the water flux of prepared composite membrane see Table 6.The configuration of surface of various films is seen accompanying drawing 5.In order to prove that there is TiO really in the film surface
2, the upper strata polymer blend film that composite membrane is compound separates and carries out the XRD test, the results are shown in Figure 6.
Table 6 different Ti O
2The time composite membrane structure and performance
| The film numbering | Preparation liquid is formed (wt%) (BPES/PVP/H 2O/TiO 2/DMAc) | Water leads to (L/m 2h) | Thickness (μ m) | Contact angle (°) |
| 14 | 10/5/0.2/8/76.5 | 859 | 155 | 68.8 |
| 15 | 10/5/0.5/8/76.8 | 945 | 160 | 63.6 |
PES and SPES blend ratio are to membrane structure and Effect on Performance
Mass ratio be blend polyethersulfone/PVP/DMAc of 10/5/85 about 45 ℃ in flask separately abundant stirring and dissolving 48h, to dissolving fully.PES and SPES mass ratio were respectively 100: 0,90: 10,80: 20 and 70: 30 in the blend polyethersulfone.Follow-up mensuration of scraping membrane process, water flux and the sign of SEM are with embodiment 1.Measurement of contact angle is with embodiment 3.The thickness of prepared composite membrane, water flux and contact angle see Table 7.The configuration of surface of various films is seen accompanying drawing 7.
Different PES of table 7. and SPES blend ratio are to the performance of composite membrane
| The film numbering | PES/SPES(wt％) | Water flux (L/m 2h) | Thickness (μ m) | Contact angle |
| 16 | 100/0 | 630 | 173 | 78.4 |
| 17 | 90/10 | 737 | 168 | 73.8 |
| 1 | 80/20 | 875 | 164 | 71.9 |
| 18 | 70/30 | 771 | 163 | 70.3 |
Embodiment 7
The SPES sulfonation degree is to membrane structure and Effect on Performance
Mass ratio be 10/5/85 blend polyethersulfone (PES: SPES=80: 20)/PVP/DMAc about 45 ℃ in flask separately abundant stirring and dissolving 48h, to dissolving fully.The sulfonation degree of SPES is respectively 5.5% and 16.2%.Follow-up mensuration of scraping membrane process, water flux and the sign of SEM are with embodiment 1.Measurement of contact angle is with embodiment 3.The thickness of prepared composite membrane, water flux and contact angle see Table 8.
The structure and the performance of composite membrane during the different sulfonation degree of table 8.
| The film numbering | Sulfonation degree (%) | Water leads to (L/m 2h) | Thickness (μ m) | Contact angle (°) |
| 1 | 5.2 | 875 | 164 | 71.9 |
| 19 | 16.2 | 626 | 163 | 66.7 |
Claims (7)
1. the preparation method of a co-mixed polyethersulfone platform complex film, the step of method is:
1) polyethersulfone blended thing 10～13wt%, additive 0.1～20wt%, deionized water 0～8wt% are dissolved in the organic solvent, heating stirs, and filters, and obtains preparation liquid after the vacuum defoamation;
2) be that 26～28 ℃ of preparation liquids are coated on the supporter of nonwoven by knifing machine with temperature, scraping film thickness is 140～180 μ m, and the cloth speed of walking of supporting layer is 1.3～1.5m/min, and the sky time of exposing to the sun is 5s;
3) supporter that will be coated with preparation liquid immerses and to solidify in the bath water, forms blend polyethersulfone/nonwoven fabrics composite film, and coagulation bath temperature is 26～28 ℃;
4) composite membrane was soaked in deionized water 5～7 days, then composite membrane is dipped in the glycerine water solution of 15～20% (v/v) and carries out hydrophilicity-imparting treatment, the processing time is 20～24h;
5) composite membrane is taken out natural airing from glycerine water solution.
2. the preparation method of a kind of co-mixed polyethersulfone platform complex film according to claim 1, it is characterized in that, described polyethersulfone blended thing is meant the blend of polyether sulfone and sulfonated polyether sulfone, and the mass ratio of polyether sulfone and sulfonated polyether sulfone is 100/0～70/30 in the preparation liquid.
3. the preparation method of a kind of co-mixed polyethersulfone platform complex film according to claim 1 is characterized in that, described organic solvent is N, N-dimethylacetylamide, N, dinethylformamide, N-methyl pyrrolidone or dimethyl sulfoxide (DMSO).
4. the preparation method of a kind of co-mixed polyethersulfone platform complex film according to claim 1 is characterized in that, described additive is one or both in polyvinylpyrrolidone or the nano titanium oxide.
5. according to the preparation method of claim 1 or 4 described a kind of co-mixed polyethersulfone platform complex films, it is characterized in that described polyvinylpyrrolidone is polyvinylpyrrolidone K30, molecular weight is 30,000, and addition is 1～20wt%.
6. according to the preparation method of claim 1 or 4 described a kind of co-mixed polyethersulfone platform complex films, it is characterized in that described nano titanium oxide is a Detitanium-ore-type, addition is 0.1～0.5wt%.
7. the preparation method of a kind of co-mixed polyethersulfone platform complex film according to claim 1 is characterized in that, described nonwoven is a polyester non-woven fabric, and thickness is 115～125 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510060289 CN1730141A (en) | 2005-08-04 | 2005-08-04 | Process for preparing co-mixed polyethersulfone platform complex film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101219350B (en) * | 2007-10-11 | 2010-06-02 | 亚美滤膜（南通）有限公司 | Method for producing hydrophilic polyethersulfone millipore filter |
| CN101810892A (en) * | 2010-04-21 | 2010-08-25 | 中国科学院长春应用化学研究所 | Method for filtering liquid medicine and application of composite membrane in filtering liquid medicine |
| CN102120148A (en) * | 2011-01-19 | 2011-07-13 | 天津大学 | Preparation method for composite film of chitosan/sulfonated polyethersulfone and polyethersulfone and application thereof |
| CN102512972A (en) * | 2011-12-09 | 2012-06-27 | 西安建筑科技大学 | Method for preparing double-surface composite flat membrane |
| CN102512996A (en) * | 2011-12-09 | 2012-06-27 | 浙江工业大学 | Silica nanoparticle blended modified polysulfone membrane and its preparation method |
| CN102560936A (en) * | 2011-12-13 | 2012-07-11 | 天邦膜技术国家工程研究中心有限责任公司 | Automatic constant-linear-speed control system of film applicator |
| CN102683731A (en) * | 2011-03-18 | 2012-09-19 | 韩国科学技术研究院 | Electrolyte membrane for fuel cell, and membrane-electrode assembly and fuel cell including the same |
| CN101664649B (en) * | 2009-09-17 | 2013-01-02 | 南京大学 | Manufacturing method of small-aperture polyether sulfone planar film for membrane bioreactor |
| CN103007775A (en) * | 2012-12-21 | 2013-04-03 | 武汉纺织大学 | Method for preparing polymer flat sheet microporous membrane |
| CN103055726A (en) * | 2013-01-25 | 2013-04-24 | 丽水学院 | Preparation method of low-pressure high-flux nanofiltration membrane |
| CN103977718A (en) * | 2014-06-06 | 2014-08-13 | 中国科学技术大学 | High-water-flux forward-osmosis composite membrane and preparation method thereof |
| CN104689725A (en) * | 2013-09-17 | 2015-06-10 | 殷逢宝 | Preparation method of composite hollow fiber membrane |
| CN104801199A (en) * | 2015-04-02 | 2015-07-29 | 昆山艾可芬能源科技有限公司 | Phase-inversion casting film solidification and drying device and phase-inversion casting film solidification and drying technology |
| CN105268335A (en) * | 2014-07-23 | 2016-01-27 | 上海一鸣过滤技术有限公司 | Preparation method of hydrophilic polyether sulfone microporous film |
| CN106345317A (en) * | 2016-08-29 | 2017-01-25 | 北京碧水源膜科技有限公司 | Preparing method for a composite membrane selectively separating ammonia nitrogen, composite membrane obtained by preparing method and application thereof |
| CN106823832A (en) * | 2017-03-24 | 2017-06-13 | 河海大学 | Intelligent integrated formula automatic scraping film device |
| CN108525531A (en) * | 2017-03-02 | 2018-09-14 | 天津工业大学 | A kind of method that non-solvent induction gel phase separation method prepares polymer blend membrane |
| CN111036100A (en) * | 2019-12-31 | 2020-04-21 | 宁波日新恒力科技有限公司 | Ultrafiltration composite membrane for treating medium-high temperature wastewater and preparation method and application thereof |
| CN111266247A (en) * | 2018-12-05 | 2020-06-12 | 广州中国科学院先进技术研究所 | Continuous flat film scraping machine |
| CN114307676A (en) * | 2022-01-18 | 2022-04-12 | 杭州科百特过滤器材有限公司 | Sulfone polymer porous liquid-stopping membrane and preparation method and application thereof |
| CN114768549A (en) * | 2022-05-24 | 2022-07-22 | 重庆再升科技股份有限公司 | High-pressure deformation resistant porous membrane capable of being used as distillation membrane and preparation method thereof |
| CN114988645A (en) * | 2022-06-17 | 2022-09-02 | 国晟生态环境科技有限公司 | Novel medical sewage treatment method and application thereof |
| CN115282793A (en) * | 2022-07-18 | 2022-11-04 | 宁夏清研高分子新材料有限公司 | PES (polyether sulfone) material as well as preparation method and application thereof |
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| CN101219350B (en) * | 2007-10-11 | 2010-06-02 | 亚美滤膜（南通）有限公司 | Method for producing hydrophilic polyethersulfone millipore filter |
| CN101664649B (en) * | 2009-09-17 | 2013-01-02 | 南京大学 | Manufacturing method of small-aperture polyether sulfone planar film for membrane bioreactor |
| CN101810892A (en) * | 2010-04-21 | 2010-08-25 | 中国科学院长春应用化学研究所 | Method for filtering liquid medicine and application of composite membrane in filtering liquid medicine |
| CN101810892B (en) * | 2010-04-21 | 2013-01-02 | 中国科学院长春应用化学研究所 | Method for filtering liquid medicine and application of composite membrane in filtering liquid medicine |
| CN102120148A (en) * | 2011-01-19 | 2011-07-13 | 天津大学 | Preparation method for composite film of chitosan/sulfonated polyethersulfone and polyethersulfone and application thereof |
| CN102683731A (en) * | 2011-03-18 | 2012-09-19 | 韩国科学技术研究院 | Electrolyte membrane for fuel cell, and membrane-electrode assembly and fuel cell including the same |
| CN102512996A (en) * | 2011-12-09 | 2012-06-27 | 浙江工业大学 | Silica nanoparticle blended modified polysulfone membrane and its preparation method |
| CN102512972B (en) * | 2011-12-09 | 2013-10-02 | 西安建筑科技大学 | Method for preparing double-surface composite flat membrane |
| CN102512996B (en) * | 2011-12-09 | 2014-06-11 | 浙江工业大学 | Silica nanoparticle blended modified polysulfone membrane and preparation method thereof |
| CN102512972A (en) * | 2011-12-09 | 2012-06-27 | 西安建筑科技大学 | Method for preparing double-surface composite flat membrane |
| CN102560936A (en) * | 2011-12-13 | 2012-07-11 | 天邦膜技术国家工程研究中心有限责任公司 | Automatic constant-linear-speed control system of film applicator |
| CN103007775A (en) * | 2012-12-21 | 2013-04-03 | 武汉纺织大学 | Method for preparing polymer flat sheet microporous membrane |
| CN103055726A (en) * | 2013-01-25 | 2013-04-24 | 丽水学院 | Preparation method of low-pressure high-flux nanofiltration membrane |
| CN104689725A (en) * | 2013-09-17 | 2015-06-10 | 殷逢宝 | Preparation method of composite hollow fiber membrane |
| CN104689725B (en) * | 2013-09-17 | 2016-08-31 | 殷逢宝 | A kind of preparation method of composite hollow fiber membrane |
| CN103977718B (en) * | 2014-06-06 | 2016-03-02 | 中国科学技术大学 | Positive osmosis composite membrane of a kind of high water flux and preparation method thereof |
| CN103977718A (en) * | 2014-06-06 | 2014-08-13 | 中国科学技术大学 | High-water-flux forward-osmosis composite membrane and preparation method thereof |
| CN105268335A (en) * | 2014-07-23 | 2016-01-27 | 上海一鸣过滤技术有限公司 | Preparation method of hydrophilic polyether sulfone microporous film |
| CN104801199A (en) * | 2015-04-02 | 2015-07-29 | 昆山艾可芬能源科技有限公司 | Phase-inversion casting film solidification and drying device and phase-inversion casting film solidification and drying technology |
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| CN106345317B (en) * | 2016-08-29 | 2018-11-20 | 北京碧水源膜科技有限公司 | A kind of composite membrane that preparation method, the preparation method of the composite membrane of Selective Separation ammonia nitrogen obtain and its application |
| CN108525531A (en) * | 2017-03-02 | 2018-09-14 | 天津工业大学 | A kind of method that non-solvent induction gel phase separation method prepares polymer blend membrane |
| CN106823832A (en) * | 2017-03-24 | 2017-06-13 | 河海大学 | Intelligent integrated formula automatic scraping film device |
| CN106823832B (en) * | 2017-03-24 | 2019-08-20 | 河海大学 | Intelligent integrated formula automatic scraping film device |
| CN111266247A (en) * | 2018-12-05 | 2020-06-12 | 广州中国科学院先进技术研究所 | Continuous flat film scraping machine |
| CN111036100B (en) * | 2019-12-31 | 2022-04-05 | 宁波日新恒力科技有限公司 | Ultrafiltration composite membrane for treating medium-high temperature wastewater and preparation method and application thereof |
| CN111036100A (en) * | 2019-12-31 | 2020-04-21 | 宁波日新恒力科技有限公司 | Ultrafiltration composite membrane for treating medium-high temperature wastewater and preparation method and application thereof |
| CN114307676A (en) * | 2022-01-18 | 2022-04-12 | 杭州科百特过滤器材有限公司 | Sulfone polymer porous liquid-stopping membrane and preparation method and application thereof |
| CN114307676B (en) * | 2022-01-18 | 2023-10-31 | 杭州科百特过滤器材有限公司 | Sulfone polymer porous liquid-stopping film and preparation method and application thereof |
| CN114768549A (en) * | 2022-05-24 | 2022-07-22 | 重庆再升科技股份有限公司 | High-pressure deformation resistant porous membrane capable of being used as distillation membrane and preparation method thereof |
| CN114988645A (en) * | 2022-06-17 | 2022-09-02 | 国晟生态环境科技有限公司 | Novel medical sewage treatment method and application thereof |
| CN114988645B (en) * | 2022-06-17 | 2023-10-10 | 国晟生态环境科技有限公司 | Medical sewage treatment method and application thereof |
| CN115282793A (en) * | 2022-07-18 | 2022-11-04 | 宁夏清研高分子新材料有限公司 | PES (polyether sulfone) material as well as preparation method and application thereof |
| CN115318116A (en) * | 2022-08-05 | 2022-11-11 | 天津工业大学 | Polyether sulfone composite membrane for green preparation of benzaldehyde and preparation method thereof |
| CN115318116B (en) * | 2022-08-05 | 2024-03-15 | 天津工业大学 | Polyether sulfone composite membrane for green preparation of benzaldehyde and preparation method thereof |
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