CN100493689C - Polyaryl ether sulphone compound separation membrane and its preparation method - Google Patents
Polyaryl ether sulphone compound separation membrane and its preparation method Download PDFInfo
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Abstract
A composite polyarylthioether sulfone composite membrane for separation purpose is prepared from polyarylthioether sulfone, hydrophilic polymer, additive, and solvent through proportionally dissolving while stirring, press filtering, vacuum defoaming to obtain filming liquid, preparing hollow fibre membrane or flat membrane, pore reserving treatment, water washing and drying. It has high tolerence to solvent and high temp.
Description
One, technical field
The present invention relates to a kind of polyaryl thioether sulfone composite separating film and preparation method thereof, belong to the preparation field of membrane material.
Two, background technology
Membrane separation technique is meant with pellicle and relies on external energy or chemical potential difference as the selectivity barrier layer, makes that some component sees through in the mixed system, and keeps other parts, thereby reaches the technology of purposes such as classification, separation, purification, enrichment.Here the film of indication is meant in a kind of liquid mutually or the thin condensed phase part of the one deck between two kinds of fluids, and can make a kind of material that produces effect of mass transmitting between these two parts.
Membrane material is to obtain by existing macromolecular material and inorganic material screening mostly at present, highly versatile, and specificity is poor.Therefore, in some special circumstances, just relatively more difficult as making the diffusion barrier that satisfies separation condition under the situations such as high temperature, high corrosion.
Polyaryl thioether sulfone Poly (arylene sulfide sulfone, PASS) chain structure repetitive is-[Ar-S-]-or high molecular polymer with this kind repetitive segment, is based on the general designation of a family macromolecule polymer of aryl sulfone and sulfide based structural in the molecular backbone structure.Polyaryl thioether sulfone includes PPSS Poly (Phenylene sulfidesulfone, PPSS), MODIFIED PP SS resin, as copolymer of sulfonation PPSS resin, chloromethylation PPSS, amination PPSS and oxidation PPSS resin and PPSS etc., when-[Ar-S-]-in-Ar-is PPSS during for diphenyl sulfone, this resin is a kind of new special engineering plastics of being succeeded in developing by U.S. Phillips oil company, historical existing more than 30 year of its research and development.As the structurally-modified material of polyphenylene sulfide (PPS), PPSS has possessed some excellent properties of polyphenylene sulfide, as good mechanics, electric property, dimensional stability and chemical resistance, radiation hardness, anti-flammability etc.; Because the strong polarity sulfuryl (SO in strand
2-), make its vitrification point (Tg) up to 215 ℃, thereby have some brand-new excellent properties, as the heat endurance more better, more excellent shock resistance and bending resistance, thereby polyphenylene sulfide glass temperature not high (Tg=85 ℃), poor toughness, shortcoming that fragility is big have been remedied than polyphenylene sulfide.Because PPSS is non-crystalline material, have fabulous stalling characteristic and corrosion resistance, thereby the diffusion barrier under severe rugged environments such as high temperature and soda acid, used of the formulations prepared from solutions that can utilize the modification of PPSS or copolymer, thereby make the poly arylidene thio-ester sulphone resin have bigger development potentiality and market prospects.
JP-A-3-209,589 have provided a kind of method of preparation PPSS hollow-fibre membrane, PPSS is dissolved in the N-methyl pyrrolidone that is added with ethylene glycol ethyl ether makes preparation liquid, make PPSS doughnut by spinning again with certain inner surface smoothness.But the PPSS that this method makes mainly is confined to the preparation of hollow-fibre membrane on the preparation method, and the goods permeability is difficult to guarantee that the scope of application is narrow.
Three, summary of the invention
The objective of the invention is provides a kind of polyaryl thioether sulfone composite separating film and preparation method thereof at the deficiencies in the prior art, to be fit to the diffusion barrier of some harsh separation conditions.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
The recipe ingredient number of polyaryl thioether sulfone composite separating film:
100-300 parts of polyaryl thioether sulfones
0-150 parts of hydrophilic polymers
1-400 parts of additives
300-900 parts of solvents
Wherein polyaryl thioether sulfone is at least a in the copolymer of PPSS, sulfonated polyphenyl thioether sulfone, chloromethylation PPSS, amination PPSS, oxidation polyphenylene sulfide sulphone resin and PPSS.
Hydrophilic polymer is any one in SPSF, cellulose, PVP, polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polyacrylic acid or the polyacrylamide.
Additive be sodium sulphate, sodium chloride, magnesium chloride, ammonium sulfate, zinc chloride, odium stearate, calcium stearate, methyl alcohol, season amylalcohol, EGME, ethylene glycol ethyl ether, dibutyl phthalate, methylcellulose, carbon molecular sieve, alundum (Al, SiO 2 molecular sieve adsorbent, two-(salicylide) ethylenediamine cobalt or palladium or platinum or nickel transistion metal compound solid catalyst, rare earth, silica, calcium carbonate, carbon black inorganic non-metallic nano particle at least a.
Solvent is dimethyl sulfoxide (DMSO), sulfolane, diphenyl sulphone (DPS), N-methyl pyrrolidone, N, at least a in dinethylformamide, dimethylacetylamide, phenol, HMPA, cyclohexanone or the tetrachloroethanes.
The coagulating bath of using in the film forming procedure can be the aqueous solution of the above-mentioned solvent of 1-50wt% or the concentration aqueous solution as the ethanol of 0-100wt%, ethylene glycol, propyl alcohol, propane diols, glycerine as concentration.
Protect the hole agent and be in ethanol, ethylene glycol, propyl alcohol, propane diols or the glycerine of 20-50wt% any.
The preparation method of polyaryl thioether sulfone composite separating film:
1, the preparation of preparation liquid
With 100-300 parts of polyaryl thioether sulfones; 0-150 parts of hydrophilic polymers; 1-400 parts of additives; 300-900 parts of solvents; Add and to have in the dissolution equipment of agitator, thermometer, in 30-80 ℃ of stirring and dissolving, solids removed by filtration impurity under 0.2-0.3MPa pressure, vacuum＜-0.5MPa deaeration 5 hours, make preparation liquid;
2, the spinning of phase transfer method hollow-fibre membrane and post processing
The preparation liquid that makes is spun into hollow-fibre membrane through dry-jet wet spinning, solvent in the nascent membrane is partly volatilized, again newborn fiber is immersed in the coagulating bath, finish solidifying of strand by double diffusion frozen glueization, after utilizing guarantor's hole agent to protect the hole processing again, remove solvent and coagulating agent in the striping through washing, air-dry operation, make membrane structure be fixed to finished product.Wherein coagulation bath temperature is 10-50 ℃; Spinning humidity is 50%-80%; Draw ratio is 1.0-3.0 times;
3, the preparation of phase transfer method flat sheet membrane and post processing
Preparation liquid is scraped on flat board equably with scraper, and the hydrostomia temperature is 20-60 ℃, and humidity is 50-80%.The solution of nascent film is partly volatilized finish the solution prevapourising, the solvent prevapourising time is 10-50 second, and solvent prevapourising temperature is 20-60 ℃, in the nascent film immersion coagulating bath, finishes solidifying of flat sheet membrane by double diffusion frozen glueization again.After the hole processing is protected in temperature 20-50 ℃ of utilization guarantor hole agent, remove solvent and coagulating agent in the striping again, make membrane structure be fixed to finished product through washing, air-dry operation;
4, the preparation of volume evaporation flat sheet membrane
Preparation liquid is scraped on flat board or supporting layer equably with scraper, kept 20-200 minute, make the solution of the nascent film film forming of all volatilizing at temperature 100-200 ℃.Wherein the hydrostomia temperature is that 20-60 ℃, hydrostomia humidity are 50-80%;
5, the preparation of oxidation polyaryl thioether sulfone diffusion barrier
The polyaryl thioether sulfone diffusion barrier that will make with aforementioned any method is at temperature 150-220 ℃, and heating is 1-10 hour in the air or oxygen, makes oxidation polyaryl thioether sulfone diffusion barrier.
The performance of polyaryl thioether sulfone diffusion barrier:
Excellent anti-solvent: for many other polysulfones diffusion barriers in the solvent environment that can't exist, as acetate, hexane, trichloro-ethylene, toluene, vinylacetic acid, acetone, dioxane etc.After prepared polyaryl thioether sulfone diffusion barrier oxidation processes, itself even the erosion that can resist strong protonic solvent such as chloroform, N-methyl pyrrolidone, dimethylacetylamide, pyrimidine.
Heat-resisting quantity: prepared diffusion barrier can be anti-at least 215 ℃ high temperature (heatproof by oxidation PPSS diffusion barrier be higher), and other common polysulfones diffusion barrier heatproof is generally about 190 ℃.
Because prepared polyaryl thioether sulfone diffusion barrier has above excellent properties, can be used for the separation process such as micro-filtration, ultrafiltration, counter-infiltration, dialysis, electrodialysis, gas separation under the particular surroundings such as high temperature, high burn into high pressure, also can be used as specific function films such as battery diaphragm, fuel cell barrier film, electrolyzer barrier film, enzyme and hydrogen-catalyst reactor be applied to above chat and particular surroundings.
Four, the specific embodiment
Below by embodiment the present invention is specifically described; be necessary that being pointed out that at this that present embodiment only is useful on further specifies the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1: the preparation of PPSS hollow-fibre membrane:
The preparation of preparation liquid:
With polyphenylene sulfide sulphone resin 180g, N-methyl pyrrolidone (NMP) 800g, zinc chloride 20g, ethylene glycol ethyl ether 20g, add in the dissolution equipment and make its dissolving, under 50 ℃, violent mechanical agitation, carry out swelling, until under 0.2MPa pressure, removing solid impurity after the dissolving fully through filter plant, preparation liquid is made in vacuum defoamation, vacuum＜-0.4MPa.
Spinning and post processing:
The preparation liquid that makes is spun into hollow fiber separating film through the dry-jet wet spinning spinning, solution in the nascent film is partly volatilized, finish the solution prevapourising, again nascent film is immersed and contain in N-methyl pyrrolidone (NMP) aqueous solution of 2wt%, finish solidifying of strand by double diffusion frozen glueization, after protecting the hole processing again, remove solvent and coagulating agent in the striping, make membrane structure be fixed to finished product through washing, air-dry operation.Wherein coagulation bath temperature is 10 ℃; Spinning humidity is 60%; Protecting the hole agent is the aqueous solution of ethylene glycol, and concentration is 20 weight %; Draw ratio is 1.7 times; Adopt concentric circles to insert the tubular type spinning head during spray silk.
Embodiment 2: the preparation of polyaryl thioether sulfone flat sheet membrane:
Being equipped with of preparation liquid:
With polyphenylene sulfide sulphone resin 175g, N, the rare aqueous solution of sodium stearate 80g of dinethylformamide 725g, 10wt%, magnesium chloride 20g, add in the dissolution equipment and make its dissolving, under 45 ℃, violent mechanical agitation, carry out swelling, until removing solid impurity through filter plant after the dissolving under 0.3MPa pressure fully, preparation liquid is made in vacuum defoamation, vacuum＜-0.5MPa.
System film: preparation liquid is scraped on flat board equably the hydrostomia temperature with scraper: 45 ℃, humidity: 65%.The solution of nascent film is partly volatilized finish the solution prevapourising, the solvent prevapourising time: 30 seconds, solvent prevapourising temperature: 30 ℃.Again nascent film is immersed in the 25wt% ethanol water, finish solidifying of flat sheet membrane by double diffusion frozen glueization.After protecting the hole processing again, remove solvent and coagulating agent in the striping, make membrane structure be fixed to finished product through washing, air-dry operation.Wherein coagulation bath temperature is 20 ℃; Protecting the hole agent is the glycerin solution of concentration 30wt%.
Embodiment 3: the preparation of PPSS composite hollow fiber membrane:
Sulfonated polyphenyl thioether sulfone 40g, PPSS are mixed oven dry 60g, be dissolved in the 400gN-methyl pyrrolidone, make spinning solution 1.
With being dissolved in the 410gN-methyl pyrrolidone after PPSS 60g, the polyvinylpyrrolidone 30g mixing oven dry, make spinning solution 2.
Remove solid impurity through filter plant under 0.2MPa pressure, preparation liquid is made in vacuum defoamation, vacuum＜-0.1MPa.
Spinning solution 1 enters interior annular distance from the interior annular distance inlet of Crossed Circle hole spinning head, sprays through interior annular distance bottom.
Spinning solution 2 enters outer annular distance from the outer annular distance inlet of Crossed Circle hole spinning head, sprays through outer annular distance bottom.
Hollow medium (water) enters the core hole from the core hole inlet of spinning head, sprays from bottom, core hole.
After the spinning solution 1 of spinning head ejection and spinning solution 2 are compound, enter the outside coagulation bath, just become composite hollow fiber membrane behind the gel.The hydrostomia temperature is 45 ℃, humidity 60%; The solvent prevapourising time is 12 seconds, and temperature is 20 ℃; 20 ℃ of coagulation bath temperatures; Protecting the hole agent is the aqueous solution of the ethylene glycol of concentration 20wt%; Draw ratio is 2.5 times.
Embodiment 4: the preparation of PPSS anion diffusion barrier
The PPSS 16g that will methylate is dissolved in and makes solution 1 in the 84gN-methyl pyrrolidone.The PPSS 18g of amination is dissolved in the 82gN-methyl pyrrolidone, makes solution 2.With solution 1 curtain coating on glass plate, be positioned over and heat in 110 ℃ of freeze-day with constant temperature baking ovens and dry 30 minutes, form a polymeric layer, again with solution 2 curtain coatings on copolymer layer, on nascent film, launch the polypropylene non-woven fabric that 0.14mm is thick then, and in 110 ℃ of freeze-day with constant temperature baking ovens heating and dry 30 minutes, product peeled off from glass plate makes a kind of double-layered compound film, with this composite membrane at trimethylamine (1.2mol/dm
3) the middle immersion, 60 ℃ of following aminations 16 hours, promptly obtain anion-exchange membrane.
Embodiment 5: the preparation of PPSS-polyphenylene sulfide ketone copolymers hollow membrane:
The preparation of preparation liquid:
Prepare a kind of homogeneous polymer solution, comprise PPSS-polyphenylene sulfide ketone copolymers 160g, polyacrylamide 30g, HMPA (HMPA) 710g, EGME 70g, sodium sulphate 30g, add in the dissolution equipment and make its dissolving, under 65 ℃, violent mechanical agitation, carry out swelling, until dissolving back process solids removed by filtration impurity under 0.3MPa pressure fully, preparation liquid is made in vacuum defoamation, vacuum＜-0.1MPa.
Spinning and post processing:
The preparation liquid that makes is spun into hollow fiber separating film through the dry-jet wet spinning spinning, solution in the nascent film is partly volatilized, finish the solution prevapourising, again nascent film is immersed and contain in the glycol water of 20wt%, finish solidifying of strand by double diffusion frozen glueization, after protecting the hole processing again, remove solvent and coagulating agent in the striping, make membrane structure be fixed to finished product through washing, air-dry operation.Wherein coagulation bath temperature is 20 ℃; Spinning humidity is 60%; Protecting the hole agent is the aqueous solution of the propane diols of concentration 25wt%; Draw ratio is 2.0 times; Adopt concentric circles to insert the tubular type spinning head during spray silk.
Embodiment 6: the preparation of catalysis-PPSS gas separation membrane
The preparation of preparation liquid:
Prepare a kind of homogeneous polymer solution, comprise polyphenylene sulfide sulphone resin 190g, phenol-tetrachloroethanes mixture (weight ratio is 3:2) 725g, two-(salicylide) ethylenediamine cobalt 100g, add in the dissolution equipment and make its dissolving, under 52 ℃, violent mechanical agitation, carry out swelling, until dissolving back process solids removed by filtration impurity under 0.2MPa pressure fully, preparation liquid is made in vacuum defoamation, vacuum＜-0.2MPa.
System film: preparation liquid is scraped on flat board equably with scraper, kept 2 hours down, make the solution of the nascent film film forming of all volatilizing, make nonporous membrane by solvent evaporated method at 120 ℃.Wherein 45 ℃ of hydrostomia temperature, hydrostomia humidity 65%.
Embodiment 7: select the preparation of adsorptivity PPSS gas separation membrane
The preparation of preparation liquid:
Prepare a kind of homogeneous polymer solution, comprise polyphenylene sulfide sulphone resin 190g, dimethyl sulfoxide (DMSO) 725g, Pd/Al
2O
3Catalyst 20g adds in the dissolution equipment and makes its dissolving, carries out swelling under 60 ℃, violent mechanical agitation, removes solid impurity through filter plant until dissolving back fully under 0.2MPa pressure, and preparation liquid is made in vacuum defoamation, vacuum＜-0.2MPa.
System film: preparation liquid is scraped on flat board equably with scraper, kept 3 hours down, make the solution of the nascent film film forming of all volatilizing, make nonporous membrane by solvent evaporated method at 150 ℃.Wherein 50 ℃ of hydrostomia temperature, hydrostomia humidity 75%.
Embodiment 8: the preparation of PPSS/nano combined flat sheet membrane:
The preparation of preparation liquid:
Prepare a kind of homogeneous polymer solution, comprise polyphenylene sulfide sulphone resin 160g, dimethyl sulfoxide (DMSO) 785g, EGME 30g, methylcellulose 20g, NdO nano particle 5g, add in the dissolution equipment and make its dissolving, under 56 ℃, violent mechanical agitation, carry out swelling, until under 0.2MPa pressure, removing solid impurity after the dissolving fully through filter plant, preparation liquid is made in vacuum defoamation, vacuum＜-0.2MPa.
System film: preparation liquid is scraped on flat board equably the hydrostomia temperature with scraper: 45 ℃, humidity: 65%.The solution of nascent film is partly volatilized finish the solution prevapourising, the solvent prevapourising time: 30 seconds, solvent prevapourising temperature: 30 ℃.Again nascent film is immersed in the 90wt% ethanol water, finish solidifying of flat sheet membrane by double diffusion frozen glueization.After protecting the hole processing again, remove solvent and coagulating agent in the striping, make membrane structure be fixed to finished product through washing, air-dry operation.Wherein coagulation bath temperature is 20 ℃; Protecting the hole agent is the glycol water of concentration 30wt%.
Embodiment 9: the preparation of oxidation PPSS hollow-fibre membrane:
Technology and flow process and technological parameter under 200 ℃ heat the diphenyl sulfide sulfone hollow-fibre membrane that makes 8 hours in baking oven with embodiment two, promptly make oxidation PPSS hollow-fibre membrane.
Claims (5)
1, polyaryl thioether sulfone composite separating film is characterized in that the recipe ingredient of this composite separating film is by weight:
100-300 parts of polyaryl thioether sulfones
0-150 parts of hydrophilic polymers
1-400 parts of additives
300-900 parts of solvents
Wherein polyaryl thioether sulfone is at least a in the copolymer of PPSS, sulfonated polyphenyl thioether sulfone, chloromethylation PPSS, amination PPSS, oxidation polyphenylene sulfide sulphone resin and PPSS.
2,, it is characterized in that hydrophilic polymer is any in SPSF, cellulose, PVP, polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polyacrylic acid or the polyacrylamide according to the described polyaryl thioether sulfone composite separating film of claim 1.
3, according to the described polyaryl thioether sulfone composite separating film of claim 1, it is characterized in that additive is a sodium sulphate, sodium chloride, magnesium chloride, ammonium sulfate, zinc chloride, odium stearate, calcium stearate, methyl alcohol, season amylalcohol, EGME, ethylene glycol ethyl ether, dibutyl phthalate, methylcellulose, carbon molecular sieve, alundum (Al, the SiO 2 molecular sieve adsorbent, two-(salicylide) ethylenediamine cobalts or palladium or platinum or nickel transistion metal compound solid catalyst, rare earth, silica, calcium carbonate, at least a in the carbon black inorganic non-metallic nano particle.
4, according to the described polyaryl thioether sulfone composite separating film of claim 1, it is characterized in that solvent is dimethyl sulfoxide (DMSO), sulfolane, diphenyl sulphone (DPS), N-methyl pyrrolidone, N, at least a in dinethylformamide, dimethylacetylamide, phenol, HMPA, cyclohexanone or the tetrachloroethanes.
5, according to the preparation method of the described polyaryl thioether sulfone composite separating film of one of claim 1-4, it is characterized in that:
(1) preparation of preparation liquid
With 100-300 parts of polyaryl thioether sulfones; 0-150 parts of hydrophilic polymers; 1-400 parts of additives; 300-900 parts of solvents; Add and to have in the dissolution equipment of agitator, thermometer, in 30-80 ℃ of stirring and dissolving, solids removed by filtration impurity under 0.2-0.3MPa pressure, vacuum＜-0.5MPa deaeration 5 hours, make preparation liquid;
(2) spinning of phase transfer method hollow-fibre membrane and post processing
The preparation liquid that makes is spun into hollow-fibre membrane through dry-jet wet spinning, solvent in the nascent membrane is partly volatilized, again newborn fiber is immersed in the coagulating bath, finish solidifying of strand by double diffusion frozen glueization, after utilizing guarantor's hole agent to protect the hole processing again, remove solvent and coagulating agent in the striping through washing, air-dry operation, make the membrane structure typing
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| CN102677194B (en) * | 2011-03-18 | 2015-04-01 | 四川得阳工程塑料开发有限公司 | Polyphenylene sulfide spinning technology |
| CN102733004B (en) * | 2012-07-06 | 2014-04-16 | 四川大学 | Hollow superfine fiber of high-performance polymer and preparation method of hollow superfine fiber |
| CN102824860A (en) * | 2012-09-10 | 2012-12-19 | 四川大学 | Preparation method of high-corrosion-resistance polyarylene sulfide sulfone separation membrane |
| CN103170259B (en) * | 2013-02-28 | 2014-12-10 | 北京工业大学 | Preparation method of alcohol permselective PDMS/BPPO (Polydimethylsiloxane/Bromide Poly(2,6-dimethyl-1,4-Phenylene Oxide)) crosslinking copolymer composite membrane |
| CN103272494B (en) * | 2013-05-30 | 2015-04-29 | 奚韶锋 | Preparation method of polyvinylidene fluoride alloy membrane for wastewater treatment during high-salinity food processing |
| CN104226129A (en) * | 2014-09-18 | 2014-12-24 | 四川大学 | Polyarylenesulfidesulfone hollow fiber and flat plate separating membrane and preparation method thereof |
| CN104209024B (en) * | 2014-09-18 | 2017-02-15 | 四川大学 | Polyarylenesulfidesulfone/sulfonated polymer composite separation membrane and preparation method thereof |
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| CN105032218B (en) * | 2015-07-20 | 2017-11-03 | 四川大学 | A kind of enhanced solvent resistant polyaryl thioether sulfone hollow-fibre membrane and preparation method thereof |
| CN105597559B (en) * | 2016-03-21 | 2018-07-17 | 四川中科兴业高新材料有限公司 | A kind of polyaryl thioether sulfone composite permeable membrane preparation method |
| CN107649102B (en) * | 2017-09-30 | 2020-06-05 | 宁波市中心血站 | Preparation method of composite hollow fiber adsorption resin |
| CN108745007A (en) * | 2018-07-06 | 2018-11-06 | 天津工业大学 | A kind of preparation method of polyphenylene sulfide sulfone/polyphenylene sulfide composite membrane |
| CN113680210B (en) * | 2021-08-17 | 2023-07-28 | 安徽智泓净化科技股份有限公司 | Nanofiltration membrane for separating low-valence ions and preparation method thereof |
| CN114432906A (en) * | 2022-02-13 | 2022-05-06 | 北京化工大学 | High-temperature-resistant alkaline water electrolysis tank composite diaphragm and preparation method thereof |
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