CN104437136A - Preparation method for strength-reinforced anti-microbial hollow fiber separating membrane - Google Patents
Preparation method for strength-reinforced anti-microbial hollow fiber separating membrane Download PDFInfo
- Publication number
- CN104437136A CN104437136A CN201410614187.4A CN201410614187A CN104437136A CN 104437136 A CN104437136 A CN 104437136A CN 201410614187 A CN201410614187 A CN 201410614187A CN 104437136 A CN104437136 A CN 104437136A
- Authority
- CN
- China
- Prior art keywords
- preparation
- membrane
- spinning
- hollow fiber
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a preparation method for a strength-reinforced anti-microbial hollow fiber separating membrane. The preparation method comprises the following steps: (1) preparing a casting liquid, namely mixing polyether sulfone, thermoplastic polyurethane, polyethylene glycol, sodium dodecyl sulfate, lithium chloride and an organic solvent in ratio by weight of (10-30) : (1-6) : (2-12) : (1-2) : (1-20) : (60-90) to a reaction kettle, heating, thermally stirring and dissolving for 10-12 hours; after the raw materials are dissolved, standing till the temperature is up to the room temperature, and adding a certain quantity of quaternary ammonium salt-acrylonitrile copolymer; starting stirring, mixing uniformly, and filtering, defoaming and purifying the obtained liquid; (2) manufacturing a hollow fiber membrane, namely extruding the prepared membrane manufacturing liquid to a spinning nozzle by utilizing a metering pump, and extruding a core liquid quantitatively to an inner needle of the spinning nozzle through the metering pump; spinning by the spinning nozzle, feeding the spun fibers to sequentially pass through a coagulating bath to be cooled and coagulated and a stretching groove to be subjected to post-treatment under the action of a fraction wheel, so as to obtain the hollow fiber membrane.
Description
Technical field
The present invention relates to a kind of preparation method strengthening the antibacterial hollow fiber separation membrane of intensity.
Background technology
Along with the growth of socioeconomic development and population, shortage of water resources, as the problem of a globalization, has become the key factor of restriction China's economy and social development, also therefore in the urgent need to developing various novel, efficient Sewage advanced treatment and reuse technology.Membrane separation technique because of its have that separative efficiency is high, equipment is simple, the advantage such as easy to operate and non-secondary pollution, be the important new and high technology solving the contemporary energy, resources and environment problem, and play far-reaching influence by the industrial technology transformation of 21 century.The membrane type cellulose acetate developed the earliest and the hybrid films of celluloid, develop film that is polyamide-based, the material such as aromatic heterocyclic, polysulfones, TPO, silicone rubber kinds afterwards in succession.Along with the extensive use of membrane technology, propose new requirement to the kind of membrane material and performance, existing membrane material can not meet instructions for use far away.By adding the additive of certain ingredients to the spinning solution of existing membrane material, the advantages of multiple material can be got up, be expand the effective method of membrane material.
Phase inversion masking is large to preparation liquid composition degree of dependence, the stuctures and properties of casting solution multicomponent system on microporous barrier be wherein made up of nonsolvent additive has conclusive impact, and the casting solution additive of research and development excellent performance is the key of producing high-quality microfiltration membranes.Conventional additive, no matter be inorganic additive (as lithium chloride, magnesium perchlorate, lithium perchlorate), or small organic molecule (as glycerine, diethylene glycol (DEG), ethanol, oxalic acid etc.) is poor with the compatibility of Polymer Solution, join in preparation liquid and can cause high-polymer molecular segment that strong crimp shrinkage occurs, form separate microphase-separated, obtained microporous barrier intensity is poor, and cause casting solution system unstable, even automatically produce precipitated phase to be separated, bring inconvenience to the preservation of casting solution and use.In Japanese Patent Publication 62-017614, describe mixing Kynoar, macromolecular pore generators polyethylene glycol, surfactant POLYSORBATE 80, the then method of inversion of phases film forming.The product rupture strength that the method obtains is not enough, and the penetration speed of pure water is slow, cannot meet the demands.And U.S. Patent No. 5514461 is attempted by adding the membrane material that the comonomer such as trichloroethylene, ethene obtains better performances in Kynoar solution.Because its additive is added by physical blending, so the water flux of film declines along with the loss of additive, after usual five months, drop to original 10%-30%.Describing the polyethylene glycol adding 7.2wt% in Japanese Patent Publication 3-71168 is the film-forming method of additive, but obtains the film of high transmission flux not yet.
The performances such as polyether sulfone (PES) is a kind of membrane material of high comprehensive performance, has higher hot strength and excellent chemical stability, blood compatibility, heat resistance, compression resistance, corrosion-resistant; The material of Chang Zuowei ultrafiltration, NF membrane, more can be used as the counterdie of composite membrane, for counter-infiltration and gas separation membrane.Along with the development of membrane technology, poly (ether sulfone) film is applied to the fields such as water treatment, blood purification, food manufacturing more and more widely.
But due to the hydrophobicity of poly (ether sulfone) film material, the particulate in membrane separating process easily and in material, colloidal particle or solute transportation generation suction-operated, be stranded in film mutually in and cause fouling membrane.For example, the surface that bacterium and microorganism are easy to be adsorbed onto film forms biomembrane, and further growth, breeding form biofouling, cause the biological pollution of film, this not only causes the decline of membrane flux, also can destroy the internal structure of film, affects separating property and the service life of film.In addition when being used as the bioabsorbable polymer material of human body, also easily there is bacterial infection, huge economic loss and great malpractice will be brought.
For the deficiency of poly (ether sulfone) film resistance tocrocking, current researcher takes to solve problem to the hydrophilic modification of material and film usually, as: Wu Kaifen etc. are by PES and SPSF mixing masking, and the hydrophily of hybrid films improves, and molecular cut off diminishes; Han etc. introduce phthalidyl on original PES molecule, form PES-C structure, improve the hydrophily of membrane material; Wu Kaifen, Li Shushen, Korean style chaste tree. the research [J] of Pes-sps Blend Membrane. Environmental Chemistry, 1993.12 (6): 458 ~ 462. //Han S.Membranes & membranesprocess [M] .New York:Plenum Press, 1986.143.But the functional polymer film by preparation with anti-microbial property rarely has report with the research improving its resistance tocrocking.
For PES film except considering its antibacterial problem, also its problems of mechanical strength must be considered.
Summary of the invention
The object of the invention is to propose a kind of preparation method strengthening the antibacterial hollow fiber separation membrane of intensity.
For reaching this object, the present invention by the following technical solutions:
Strengthen a preparation method for the antibacterial hollow fiber separation membrane of intensity, the preparation method of this diffusion barrier comprises:
(1) preparation of solution is cast
By polyether sulfone, thermoplastics type's Polyurethane, polyethylene glycol, dodecyl sodium sulfate, lithium chloride, organic solvent, by weight, 10-30: 1-6: 2-12: 1-2: 1-20: 60-90 mixes in reactor, and then intensification thermal agitation is dissolved, and the time is 10-12 hour; After above-mentioned raw materials dissolves, leave standstill and reach after room temperature until temperature, add a certain amount of quaternary ammonium salt-acrylonitrile copolymer; Start stirring, mixing, then gained solution is carried out filter, deaeration purification;
(2) making of hollow-fibre membrane
Preparation liquid is clamp-oned spinning head by measuring pump by the preparation liquid that step (1) is obtained, by measuring pump, core liquid is quantitatively clamp-oned pin in spinning head; By spinning head spinning, under the effect of traction wheel, the post processing of coagulating bath cooled and solidified and stretch slot is passed through in spinning successively, obtains hollow-fibre membrane.
The fracture strength of described hollow-fibre membrane is 2.5-3.0MPa, and the pure water flux when 25 DEG C of 0.1MPa is 1500 ~ 2500L/m2.h, and porosity is 85 ~ 90%, and the average pore size of film is 0.1 μm ~ 1nm.。
Described organic solvent is dimethyl sulfoxide (DMSO), dimethyl formamide, dimethylacetylamide or 1-METHYLPYRROLIDONE.
The preparation method of described quaternary ammonium salt-acrylonitrile copolymer (PQA-co-AN), comprising:
(1) synthesis of polymerizability quaternary ammonium salt monomer (PQA)
Acetone, p-chloromethyl styrene and Dodecyl Dimethyl Amine is added in the three-necked bottle of 250mL that agitator, reflux condenser and thermometer are housed, its weight ratio is: 30-60:3-6:4-8, under agitation be heated to acetone reflux, yellow emulsion is obtained after reaction 2h, then with normal heptane, product is precipitated out, and with acetone washing 3-5 time, the product vacuum leached is dried to constant weight, obtains yellow powder;
(2) synthesis of quaternary ammonium salt-acrylonitrile copolymer (PQA-co-AN)
In the four-hole boiling flask of 250mL that agitator, thermometer, dropping funel and reflux condensing tube are housed, add the solvent dimethylacetylamide (DMAC) of 100mL and pass into nitrogen, under agitation be warming up to 65 DEG C, the polymerizability quaternary ammonium salt monomer (PQA) be dissolved in residual solvent, acrylonitrile (AN) and initiator A IBN are slowly added drop-wise in reactor, insulation polymerization 5h, cooling cessation reaction, obtains yellowish red color emulsion.Then by deionized water, product is precipitated out, and washs three times with DMAC, isolated product vacuum is dried to constant weight, obtain yellowish red color powder.
Detailed description of the invention
Embodiment 1
(1) preparation of solution is cast
By polyether sulfone, thermoplastics type's Polyurethane, polyethylene glycol, dodecyl sodium sulfate, lithium chloride, dimethyl sulfoxide (DMSO), by weight, in reactor in mix at 10: 1: 2: 1: 1: 60, and then intensification thermal agitation is dissolved, and the time is 12 hours; After above-mentioned raw materials dissolves, leave standstill and reach after room temperature until temperature, add a certain amount of quaternary ammonium salt-acrylonitrile copolymer; Start stirring, mixing, then gained solution is carried out filter, deaeration purification;
(2) making of hollow-fibre membrane
Preparation liquid is clamp-oned spinning head by measuring pump by the preparation liquid that step (1) is obtained, by measuring pump, core liquid is quantitatively clamp-oned pin in spinning head; By spinning head spinning, under the effect of traction wheel, the post processing of coagulating bath cooled and solidified and stretch slot is passed through in spinning successively, obtains hollow-fibre membrane.
The fracture strength of described hollow-fibre membrane is 3.0MPa, and the pure water flux when 25 DEG C of 0.1MPa is 2500L/m2.h, and porosity is 90%, and the average pore size of film is 1nm.
Embodiment 2
(1) preparation of solution is cast
By polyether sulfone, thermoplastics type's Polyurethane, polyethylene glycol, dodecyl sodium sulfate, lithium chloride, dimethyl formamide, by weight, in reactor in mix at 30 :-6: 2: 2: 20: 90, and then intensification thermal agitation is dissolved, and the time is 12 hours; After above-mentioned raw materials dissolves, leave standstill and reach after room temperature until temperature, add a certain amount of quaternary ammonium salt-acrylonitrile copolymer; Start stirring, mixing, then gained solution is carried out filter, deaeration purification;
(2) making of hollow-fibre membrane
Preparation liquid is clamp-oned spinning head by measuring pump by the preparation liquid that step (1) is obtained, by measuring pump, core liquid is quantitatively clamp-oned pin in spinning head; By spinning head spinning, under the effect of traction wheel, the post processing of coagulating bath cooled and solidified and stretch slot is passed through in spinning successively, obtains hollow-fibre membrane.
The fracture strength of described hollow-fibre membrane is 2.5MPa, and the pure water flux when 25 DEG C of 0.1MPa is 2000L/m2.h, and porosity is 85%, and the average pore size of film is 0.5nm.
Embodiment 3
(1) preparation of solution is cast
By polyether sulfone, thermoplastics type's Polyurethane, polyethylene glycol, dodecyl sodium sulfate, lithium chloride, dimethylacetylamide, by weight, in reactor in mix at 20: 4: 2: 1: 10: 90, and then intensification thermal agitation is dissolved, and the time is 11 hours; After above-mentioned raw materials dissolves, leave standstill and reach after room temperature until temperature, add a certain amount of quaternary ammonium salt-acrylonitrile copolymer; Start stirring, mixing, then gained solution is carried out filter, deaeration purification;
(2) making of hollow-fibre membrane
Preparation liquid is clamp-oned spinning head by measuring pump by the preparation liquid that step (1) is obtained, by measuring pump, core liquid is quantitatively clamp-oned pin in spinning head; By spinning head spinning, under the effect of traction wheel, the post processing of coagulating bath cooled and solidified and stretch slot is passed through in spinning successively, obtains hollow-fibre membrane.
The fracture strength of described hollow-fibre membrane is 2.8MPa, and the pure water flux when 25 DEG C of 0.1MPa is 1900L/m2.h, and porosity is 85 ~ 90%, and the average pore size of film is 0.1 μm.
Claims (3)
1. strengthen a preparation method for the antibacterial hollow fiber separation membrane of intensity, it is characterized in that comprising:
(1) preparation of solution is cast
By polyether sulfone, thermoplastics type's Polyurethane, polyethylene glycol, dodecyl sodium sulfate, lithium chloride, organic solvent, by weight, 10-30: 1-6: 2-12: 1-2: 1-20: 60-90 mixes in reactor, and then intensification thermal agitation is dissolved, and the time is 10-12 hour; After above-mentioned raw materials dissolves, leave standstill and reach after room temperature until temperature, add a certain amount of quaternary ammonium salt-acrylonitrile copolymer; Start stirring, mixing, then gained solution is carried out filter, deaeration purification;
(2) making of hollow-fibre membrane
Preparation liquid is clamp-oned spinning head by measuring pump by the preparation liquid that step (1) is obtained, by measuring pump, core liquid is quantitatively clamp-oned pin in spinning head; By spinning head spinning, under the effect of traction wheel, the post processing of coagulating bath cooled and solidified and stretch slot is passed through in spinning successively, obtains hollow-fibre membrane.
2. preparation method according to claim 1, it is characterized in that: the fracture strength of described hollow-fibre membrane is 2.5-3.0MPa, pure water flux when 25 DEG C of 0.1MPa is 1500 ~ 2500L/m2.h, and porosity is 85 ~ 90%, and the average pore size of film is 0.1 μm ~ 1nm.
3. preparation method according to claim 1, is characterized in that: described organic solvent is dimethyl sulfoxide (DMSO), dimethyl formamide, dimethylacetylamide or 1-METHYLPYRROLIDONE.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410614187.4A CN104437136A (en) | 2014-11-04 | 2014-11-04 | Preparation method for strength-reinforced anti-microbial hollow fiber separating membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410614187.4A CN104437136A (en) | 2014-11-04 | 2014-11-04 | Preparation method for strength-reinforced anti-microbial hollow fiber separating membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104437136A true CN104437136A (en) | 2015-03-25 |
Family
ID=52884348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410614187.4A Pending CN104437136A (en) | 2014-11-04 | 2014-11-04 | Preparation method for strength-reinforced anti-microbial hollow fiber separating membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104437136A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3162430A1 (en) * | 2015-10-27 | 2017-05-03 | Basf Se | Process for the preparation of a membrane which comprises a polyethersulfone polymer and a polyurethane polymer |
| CN108430610A (en) * | 2015-12-28 | 2018-08-21 | 东丽株式会社 | Hollow fiber membrane module and its method of operation |
| CN116589681A (en) * | 2023-07-17 | 2023-08-15 | 富海(东营)新材料科技有限公司 | Sulfonated polyether sulfone as well as preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101396642A (en) * | 2008-10-24 | 2009-04-01 | 东华大学 | Antibiotic hollow fiber separation film and preparation method thereof |
| CN101623604A (en) * | 2009-07-29 | 2010-01-13 | 四川大学 | Preparation method of hollow-fiber membrane with high intensity and high flux and additive thereof |
| CN102019150A (en) * | 2010-12-21 | 2011-04-20 | 惠州七芯膜净化环保有限公司 | Polyether sulfone-polyurethane blend hollow fiber membrane and preparation method thereof |
-
2014
- 2014-11-04 CN CN201410614187.4A patent/CN104437136A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101396642A (en) * | 2008-10-24 | 2009-04-01 | 东华大学 | Antibiotic hollow fiber separation film and preparation method thereof |
| CN101623604A (en) * | 2009-07-29 | 2010-01-13 | 四川大学 | Preparation method of hollow-fiber membrane with high intensity and high flux and additive thereof |
| CN102019150A (en) * | 2010-12-21 | 2011-04-20 | 惠州七芯膜净化环保有限公司 | Polyether sulfone-polyurethane blend hollow fiber membrane and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3162430A1 (en) * | 2015-10-27 | 2017-05-03 | Basf Se | Process for the preparation of a membrane which comprises a polyethersulfone polymer and a polyurethane polymer |
| CN108430610A (en) * | 2015-12-28 | 2018-08-21 | 东丽株式会社 | Hollow fiber membrane module and its method of operation |
| CN108430610B (en) * | 2015-12-28 | 2021-04-09 | 东丽株式会社 | Hollow fiber membrane module and method for operating same |
| US11141698B2 (en) | 2015-12-28 | 2021-10-12 | Toray Industries, Inc. | Hollow fiber membrane module and method for operating same |
| CN116589681A (en) * | 2023-07-17 | 2023-08-15 | 富海(东营)新材料科技有限公司 | Sulfonated polyether sulfone as well as preparation method and application thereof |
| CN116589681B (en) * | 2023-07-17 | 2023-09-12 | 富海(东营)新材料科技有限公司 | Sulfonated polyether sulfone as well as preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103706266B (en) | In-situ polymerization micro-PVPP modified poly (ether-sulfone) hollow-fibre membrane and its production and use | |
| CN101569837B (en) | Polyvinylidene fluoride microporous film preparation method | |
| CN102397760B (en) | Polyether sulfone hollow fiber ultrafiltration membrane and preparation method thereof | |
| CN102432782B (en) | Amphiphilic triblock copolymer, preparation method thereof, and polyethersulfone hollow fiber membrane blend-modified by using amphiphilic triblock copolymer | |
| CN105032220B (en) | Preparation method of permanent hydrophilic type polysulfone ultrafiltration membrane | |
| CN101396642B (en) | Antibiotic hollow fiber separation film and preparation method thereof | |
| CN111514768B (en) | Solvent-resistant polymer nanofiltration membrane as well as preparation method and application thereof | |
| CN102806022A (en) | Method for preparing polyacrylonitrile (PAN)-base microporous membrane | |
| CN103897309A (en) | Preparation method of high-temperature-resisting fluorine-containing polymer cellular material | |
| CN103861480A (en) | Preparation method of hydrophilic polyvinylidene fluoride flat sheet membrane and hollow fiber membrane | |
| CN102824859B (en) | Method for preparing hollow fiber nanofiltration membrane by using thermally induced phase separation/interface cross linking synchronization method | |
| CN104437136A (en) | Preparation method for strength-reinforced anti-microbial hollow fiber separating membrane | |
| CN102716677B (en) | A kind of polyvinylidene fluoride (PVDF) ultrafiltration membrane and preparation method thereof | |
| CN101791527B (en) | Terpolymer blending modified polyether sulphone (PES) hollow fiber membrane and preparation method as well as application thereof | |
| CN109012214A (en) | A method of high-permeability ultrafiltration membrane is prepared based on chemical pore-forming | |
| CN101402023A (en) | Antimicrobial flat-plate separation film and method of producing the same | |
| CN107866155A (en) | A kind of method that polymer matrix MOFs hollow fiber ultrafiltration membranes are prepared using thermally induced phase separation | |
| CN105879696A (en) | High-hydrophilic internal pressure type polysulfone/sulfonate polysulfone hollow fiber ultrafiltration membrane and preparation method thereof | |
| CN101623604B (en) | Preparation method of hollow-fiber membrane with high intensity and high flux and additive thereof | |
| CN110170250A (en) | A kind of degradable poly lactic acid/cellulose-acetafolic and preparation method thereof | |
| CN102784563A (en) | High-strength polyvinyl chloride hollow fiber ultrafilter membrane and its preparation method | |
| CN103894078A (en) | High-flux polyvinylidene fluoride hollow fiber film and preparation method thereof | |
| CN101837252B (en) | Polyacrylonitrile/polyvinylidene fluoride alloy hollow fiber membrane and preparation method thereof | |
| CN105582821A (en) | Membrane casting solution of functionalized graphene composite ultrafiltration membrane and preparation method of functionalized graphene composite ultrafiltration membrane | |
| CN106560231B (en) | A kind of method that fumed silica prepares PVC microfiltration membranes as pore-foaming agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150325 |