CN1314763C - Polysulfone porous microsphere and membrane and preparation method and use thereof - Google Patents
Polysulfone porous microsphere and membrane and preparation method and use thereof Download PDFInfo
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- CN1314763C CN1314763C CNB2003101108551A CN200310110855A CN1314763C CN 1314763 C CN1314763 C CN 1314763C CN B2003101108551 A CNB2003101108551 A CN B2003101108551A CN 200310110855 A CN200310110855 A CN 200310110855A CN 1314763 C CN1314763 C CN 1314763C
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Abstract
The present invention relates to a polysulphone multi-hole microsphere and a membrane, a manufacturing method thereof and the function thereof. The manufacturing method is characterized in that 5 to 25 shares of polysulphone, 75 to 95 shares of solvent and 0 to 5 shares of additive, all of which are added into a container, are stirred and dissolved for 2 to 24 hours at the temperature of 75 to 95DEG C; polysulphone solution obtained through deforming and slaking is manufactured into a multi-hole microsphere or a flat plate membrane by the injection of a single hole spinneret or flat glass, or is woven into a polysulphone hollow fiber membrane. The polysulphone multi-hole microsphere or membrane can be directly used on adsorbing columns or can be manufactured into an ultrafiltration membrane assembly for selectively removing environmental hormone substances. The removing rate of environmental hormone substances is 0.2 to 50 mg/g.
Description
One, technical field
The present invention relates to a kind of polysulfones porous microsphere and film and its production and use, belong to the features polymeric material field.
Two, background technology
Polysulfones (Polysulfone, be called for short PSf) be a kind of of special engineering plastics, because its second-order transition temperature height, the materialization good stability, it is a kind of engineering speciality polymer material of excellence, but as the removing material of environmental hormone, and be made into microballoon or film, still do not have research report and product both at home and abroad so far and come out." environmental hormone " speech is to be reported by U.S.'s " Boston environment " in 1996 in institute's work " bereft future " book such as reporter Anda Ma Nuosiji at first to put forward.Environmental hormone is Environmental Hormone again, and hormone confuses element, or element is confused in internal secretion.The existence of Environmental Hormone material in food, water and soil earth become worldwide problem.Environmental Hormone will be had an effect under extremely low concentration.Environmental Hormone enters after being carried in human body and the cell combine, and will send error message in vivo, thereby destroy the normal metabolism of organism, secretion and reproduction function.
The removing of Environmental Hormone material can be passed through diverse ways, selective clearing.The Environmental Hormone material can with hydrophobic polydimethylsiloxane film by film pervaporation (Pervaporation) process remove (people such as A.Higuchi, J.Membr.Sci., 2002,198:311).Membrane ultrafiltration also can be used for the isolating environment hormone.Discover with polyethersulfone-polyvinylpyrrolidone (PES-PVP) film, adopt the isolated ultrafiltration process can remove polyphenyl phenol in the Sucus Mali pumilae (people such as Z.Borneman, Separation and purification technology, 2001,22-23:53).Other method is to make Environmental Hormone degraded: the bacterium that distributes in the river some Environmental Hormone material of can degrading.People such as Kang isolate bacterium from river, and have investigated the degradation process of dihydroxyphenyl propane under aerobic and oxygen free condition; Result of study shows, and dihydroxyphenyl propane degraded rapidly under aerobic conditions (people such as J.H.Kang, Arch.Environ.Contam.Toxicol, 2002,43:265).Thereby utilize the hydridization bio-reactor also can make benzene degraded remove (people such as S.J.Yeon, ProcessBiochemistry, 1999,34:282).Adopting the method removing Environmental Hormone of absorption is a kind of very convenient and effective means.Uviolizing makes duplex DNA crosslinked, this insoluble DNA film can selective clearing have two dimensional structure the Environmental Hormone material (people such as M.Yamadad, Environ.Sci.Technol., 2001,36:949).Hydrophobic polydimethylsiloxane film also selective adsorption Environmental Hormone material (people such as B.O.Yoon, J.Membr.Sci., 2003,213:137).Adopting the method for absorption is more effective and easy method, and DNA is very expensive, and polydimethylsiloxane film adsorption effect is not good enough.
Three, summary of the invention
The objective of the invention is provides a kind of polysulfones porous microsphere and film and its production and use at the deficiencies in the prior art.Be characterized in polysulfones is mixed with solution, inject non-solvent by injection showerhead and become microballoon; Or make film, and be used for selective clearing Environmental Hormone material sphere.It is easy to have preparation, operation easily, and to the clearance rate height of Environmental Hormone material, selectivity is good.
Purpose of the present invention is realized that by following technical scheme wherein said raw material umber is parts by weight except that specified otherwise.
The recipe ingredient of polysulfones porous microsphere and film is:
The polysulfones molecular weight is 20000～50,000 5～25 parts
75～95 parts of solvents
0～5 part of additive
Solvent is N-methyl-pyrrolidone, N,N-DIMETHYLACETAMIDE, dimethyl formamide, and/or at least a in the dimethyl sulfoxide (DMSO).
Additive is a polyoxyethylene glycol, polyvinylpyrrolidone, and/or at least a in the propylene glycol.
The manufacture method of polysulfones (PSf) porous microsphere and film:
1. the preparation of polysulfones solution
With 5～25 parts of polysulfones, 75～95 parts of solvents, additive is put into container for 0～5 part, and under agitation in 75～95 ℃ of dissolvings of temperature 2～24 hours, deaeration is after filtration placed " slaking " and is made polysulfones solution.
2. the preparation of porous microsphere
Polysulfones solution is injected non-solvent by single hole spinning nozzle or injection needles, and stir, obtain the polysulfones porous microsphere, its diameter is 1～3mm.
3. the preparation of porous flat plate film
Polysulfones solution is tiled on the sheet glass, placed in air 1～60 minute, form nascent film, the symphysis of will coming into being is then put into the non-solvent film forming together with sheet glass, and its film thickness is 0.1～2mm.
4. the preparation of porous hollow fiber membrane
With the press filtration of polysulfones solution, and extrude through two concentrically ringed tubular fibre spinning nozzle with volume pump, the spinning solution extruded velocity is 3～15ml/min; Nascent fibre in air through 5～50cm apart from after in 20～50 ℃ of water-baths of temperature coagulation forming; Reel through the plasticizing-bath drawing-off, speed is 5～50m/min again, then gets the PSf hollow-fibre membrane, and its internal diameter is 200～1000 μ m, and wall thickness is 50～500 μ m.
5. the aftertreatment of microballoon and film
Microballoon or film are removed residual solvent and additive 50～90 ℃ of poach of temperature 20～60 minutes.The porosity of its microballoon and film is 30～95%.
The purposes of polysulfones porous microsphere and film
Polysulfones can directly be prepared into the microballoon adsorption column, perhaps makes ultra-filtration membrane and uses in ultra-filtration process, selective clearing Environmental Hormone material.
1. the preparation of adsorption column is filled in the separation adsorption column with microballoon, and volume can be adjusted as required, preparation microballoon adsorption column; Flat sheet membrane can directly be used, and uses during ultrafiltration, also can be cut into certain volume and fill the preparation adsorption column; Hollow-fibre membrane is isometric to be cut off, and obtains hollow core staple fibers and fills the preparation adsorption column, and hollow-fibre membrane also can be directly used in absorption or use by ultrafiltration.
2. polysulfones porous microsphere and film are used for selective adsorption Environmental Hormone material.Octanol-water partition coefficient LogP
OWGreater than 1.5 all can adsorption removal, and Log P
OWNumerical value is bigger, and clearance rate is higher.To the clearance rate of Environmental Hormone material (the milligram number of every gram polysulfones microballoon or film absorption Environmental Hormone material) at 0.2～50mg/g.The clearance rate of component environment hormone material sees table 1 for details.
The present invention has following advantage:
1. the material materialization good stability that adopts of polysulfones porous microsphere and film, corrosion such as acid and alkali-resistance.The special engineering plastics polysulfones is applied to the environmental purification field, removes the very big Environmental Hormone material of human body harm.
2. the polysulfones porous microsphere and the film that obtain of the present invention can be directly used in selective adsorption Environmental Hormone material, also can make the form of adsorption column, the adsorption column adsorption efficiency height of making, and simple to operate, cost is low.
3. the present invention adopts the technological line of oneself, and polysulfones is made porous microsphere and film, is applied to selective clearing Environmental Hormone material, has filled up domestic blank.
Four, embodiment
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; 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 foregoing invention.
1. with polysulfones 20 grams, polyoxyethylene glycol 0.1 restrains, and N-Methyl pyrrolidone 79.9 grams stir 4 hours mixings down for 90 ℃ in temperature.Injection needles by 1mm stirs under 100rpm speed in the entry of polysulfones drips of solution.The microballoon that obtains is that diameter is 2.7mm, removes residual solvent through poach, makes adsorption column, is 6mg/g to the removing amount of biphenyl.
2. with polysulfones 10 grams, dimethyl formamide 90 grams stir 6 hours mixings down for 90 ℃ in temperature.Injection needles by 0.4mm stirs under 100rpm speed in the entry of polysulfones drips of solution.The diameter of micro ball that obtains is 1.9mm, removes residual solvent through poach, makes adsorption column, is 28mg/g to the removing amount of dibenzofuran.
3. with polysulfones 15 grams, polyvinylpyrrolidone 3 restrains, and dimethyl sulfoxide (DMSO) 82 grams stir 12 hours mixings down for 90 ℃ in temperature.Polysulfones solution is tiled on the sheet glass, placed 15 minutes in air, form nascent film, the symphysis of will coming into being is then put into non-solvent together with sheet glass and is become flat sheet membrane, and its film thickness is 0.5mm.The removing amount that hexichol-p-two is disliked pod is 8mg/g.
4. with polysulfones 18 grams, polyvinylpyrrolidone 2 restrains, and N,N-DIMETHYLACETAMIDE 80 grams stir 6 hours mixings down for 90 ℃ in temperature.Become spinning solution through the press filtration deaeration, and extrude through two concentrically ringed tubular fibre spinning nozzle with volume pump, spinning solution extruded velocity 6ml/min, apart from 30cm, reel through the plasticizing-bath drawing-off again by coagulation forming in 30 ℃ of water-baths of temperature at air section for newborn fiber, winding speed 30m/min, being spun into hollow-fibre membrane, making the hollow core staple fibers adsorption column again, is 11mg/g to the removing amount of dibenzofuran.
Table 1 polysulfones porous microsphere and film are to the clearance rate of component environment hormone material
| Environmental Hormone material Chinese | Environmental Hormone material english abbreviation | Clearance rate (mg/g) |
| Biphenyl dibenzofuran hexichol-p-two dislikes pod dihydroxyphenyl propane stilboestrol | BP DBF DBD BPA DES | 10～25 12～30 5～30 0.5～5 1～5 |
Annotate: clearance rate is the milligram number of the adsorbed Environmental Hormone material of every gram polysulfones microballoon or film.
Claims (13)
1. polysulfones porous microsphere is characterized in that the recipe ingredient of this porous microsphere is by weight:
The polysulfones molecular weight is 20000～50,000 2～25 parts
75～95 parts of solvents
0～5 part of additive
The preparation of polysulfones porous microsphere
(1) preparation of polysulfones stoste
With 5～25 parts of polysulfones, 75～95 parts of solvents, additive is put into container for 0～5 part, under agitation in 75～95 ℃ of temperature dissolving 2～24 hours, after filtration, deaeration, placement " slaking " obtain polysulfones stoste,
(2) preparation of porous microsphere
Above-mentioned polysulfones stoste by single hole spinning nozzle or injection needles, is injected non-solvent, and stir, preparation polysulfones porous microsphere, its diameter is 1～3mm, porosity is 30～95%.
2. according to the described polysulfones porous microsphere of claim 1, it is characterized in that solvent is a N-Methyl pyrrolidone, N,N-DIMETHYLACETAMIDE, at least a in dimethyl formamide and/or the dimethyl sulfoxide (DMSO).
3. according to the described polysulfones porous microsphere of claim 1, it is characterized in that additive is a polyoxyethylene glycol, at least a in polyvinylpyrrolidone and/or the propylene glycol.
4. polysulfones porous-film is characterized in that the recipe ingredient of this porous-film is by weight:
The polysulfones molecular weight is 20000～50,000 2～25 parts
75～95 parts of solvents
0～5 part of additive
One of polysulfones porous-film preparation
(1) preparation of polysulfones stoste
With 5～25 parts of polysulfones, 75～95 parts of solvents, additive is put into container for 0～5 part, under agitation in 75～95 ℃ of temperature dissolving 2～24 hours, after filtration, deaeration, placement " slaking " obtain polysulfones stoste,
(2) preparation of porous flat plate film
Above-mentioned polysulfones stoste is tiled on the sheet glass, placed in air 1～6 minute, become nascent film, the symphysis of will coming into being is then put into the non-solvent film forming together with sheet glass, and its film thickness is 0.1～2mm, and porosity is 30～95%;
Two of polysulfones porous-film preparation
(1) preparation of polysulfones stoste
With 5～25 parts of polysulfones, 75～95 parts of solvents, additive is put into container for 0～5 part, under agitation in 75～95 ℃ of temperature dissolving 2～24 hours, after filtration, deaeration, placement " slaking " obtain polysulfones stoste,
(2) preparation of porous hollow fiber membrane
With the press filtration of above-mentioned polysulfones stoste, and extrude by two concentrically ringed tubular fibre spinning nozzle with volume pump, the spinning solution extruded velocity is 3～15ml/mim; Nascent fibre in air through 5～50cm apart from after be coagulation forming in 20～50 ℃ of water-baths in temperature; Reel through the plasticizing-bath drawing-off, speed is 5～50m/min again, obtains ps hollow fiber uf membrane, internal diameter 200～1000 μ m of its hollow-fibre membrane, film thickness 50～500 μ m, porosity 30～95%.
5. according to the described polysulfones porous-film of claim 4, it is characterized in that solvent is a N-Methyl pyrrolidone, N,N-DIMETHYLACETAMIDE, at least a in dimethyl formamide and/or the dimethyl sulfoxide (DMSO).
6. according to the described polysulfones porous-film of claim 4, it is characterized in that additive is a polyoxyethylene glycol, at least a in polyvinylpyrrolidone and/or the propylene glycol.
7. according to the manufacture method of the described polysulfones porous microsphere of claim 1, it is characterized in that:
(1) preparation of polysulfones stoste
With 5～25 parts of polysulfones, 75～95 parts of solvents, additive is put into container for 0～5 part, under agitation in 75～95 ℃ of temperature dissolving 2～24 hours, after filtration, deaeration, placement " slaking " obtain polysulfones stoste,
(2) preparation of porous microsphere
Above-mentioned polysulfones stoste by single hole spinning nozzle or injection needles, is injected non-solvent, and stir, preparation polysulfones porous microsphere, its diameter is 1～3mm,
(3) aftertreatment of porous microsphere
To remove residual solvent and additive, the porosity of its microballoon was 30～95% to microballoon 50～90 ℃ of poach of temperature 20～60 minutes.
8. according to the preparation method of the described polysulfones porous microsphere of claim 7, it is characterized in that non-solvent is at least a in the aqueous solution of water, alcohols and/or polysulfones solvent.
9. according to the manufacture method of the described polysulfones porous-film of claim 4, it is characterized in that:
(1) preparation of polysulfones stoste
With 5～25 parts of polysulfones, 75～95 parts of solvents, additive is put into container for 0～5 part, under agitation in 75～95 ℃ of temperature dissolving 2～24 hours, after filtration, deaeration, placement " slaking " obtain polysulfones stoste,
(2) preparation of porous flat plate film
Above-mentioned polysulfones stoste is tiled on the sheet glass, placed in air 1～6 minute, become nascent film, the symphysis of will coming into being is then put into the non-solvent film forming together with sheet glass, and its film thickness is 0.1～2mm,
(3) aftertreatment of porous flat plate film
To remove residual solvent and additive, the porosity of its film was 30～95% to film 50～90 ℃ of poach of temperature 20～60 minutes.
10. according to the preparation method of the described polysulfones porous-film of claim 9, it is characterized in that non-solvent is at least a in the aqueous solution of water, alcohols and/or polysulfones solvent.
11. the preparation method according to the described polysulfones porous-film of claim 4 is characterized in that:
(1) preparation of polysulfones stoste
With 5～25 parts of polysulfones, 75～95 parts of solvents, additive is put into container for 0～5 part, under agitation in 75～95 ℃ of temperature dissolving 2～24 hours, after filtration, deaeration, placement " slaking " obtain polysulfones stoste,
(2) preparation of porous hollow fiber membrane
With the press filtration of above-mentioned polysulfones stoste, and extrude by two concentrically ringed tubular fibre spinning nozzle with volume pump, the spinning solution extruded velocity is 3～15ml/mim; Nascent fibre in air through 5～50cm apart from after be coagulation forming in 20～50 ℃ of water-baths in temperature; Reel through the plasticizing-bath drawing-off, speed is 5～50m/min again, obtains ps hollow fiber uf membrane, internal diameter 200～1000 μ m of its hollow-fibre membrane, and film thickness 50～500 μ m,
(3) aftertreatment of porous hollow fiber membrane
To remove residual solvent and additive, the porosity of its film was 30～95% to film 50～90 ℃ of poach of temperature 20～60 minutes.
12., it is characterized in that non-solvent is at least a in the aqueous solution of water, alcohols and/or polysulfones solvent according to the preparation method of the described polysulfones porous-film of claim 11.
13. purposes according to claim 1 or 4 described polysulfones porous microspheres and film, it is characterized in that adsorption column that this microballoon and film are made or the ultra-filtration membrane of making use in ultra-filtration process, being used for selective clearing Environmental Hormone material, is 0.2～50mg/g to the clearance rate of Environmental Hormone material.
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| CN103551128A (en) * | 2013-11-15 | 2014-02-05 | 哈尔滨工业大学 | Method for preparing adsorption resin through adopting nonsolvent-induced phase separation method |
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