CN101396642B - Antibiotic hollow fiber separation film and preparation method thereof - Google Patents
Antibiotic hollow fiber separation film and preparation method thereof Download PDFInfo
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- CN101396642B CN101396642B CN2008102017637A CN200810201763A CN101396642B CN 101396642 B CN101396642 B CN 101396642B CN 2008102017637 A CN2008102017637 A CN 2008102017637A CN 200810201763 A CN200810201763 A CN 200810201763A CN 101396642 B CN101396642 B CN 101396642B
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Abstract
The invention relates to an antibacterial hollow fiber separation membrane and a preparation method thereof. The membrane comprises polyether sulfone, quaternary ammonium salt-acrylonitrile copolymer, pore-forming agent and organic solvent with the weight ratio of 10-30 to 1-10 to 1-20 to 60-90. The preparation method comprises: (1) the preparation of casting liquid: the polyether sulfone, the quaternary ammonium salt-acrylonitrile copolymer, the pore-forming agent and the organic solvent are mixed and the raw materials are put in a dissolution reactor to be filtered, deaerated and purified; (2) the preparation of the hollow fiber membrane: in the spinning process, a dry-jet wet spinning method is adopted for the molding. After the dry-spinning process of 50-500mm, primary hollow fiber membrane is formed through solidification in coagulation bath. After drawing, washing, winding, hole preserved processing and drying, blending hollow fiber membrane provided by the invention is obtained. The prepared separation membrane has the advantages of high mechanical strength, good destruction resistance performance, good physical stability and chemical stability and long service life.
Description
Technical field
The invention belongs to the organic separation membrane preparation field, particularly relate to a kind of antibacterial hollow fiber separation membrane and preparation method thereof.
Background technology
Performances such as polyether sulfone (PES) is a kind of membrane material of high comprehensive performance, has higher draw tensile strength and excellent chemical stability, blood compatibility, hear resistance, compression resistance, and is corrosion-resistant; The material of Chang Zuowei ultrafiltration, NF membrane more can be used as the counterdie of composite membrane, is used for counter-infiltration and gas separation membrane.Along with the development of membrane technology, poly (ether sulfone) film has been applied to fields such as water treatment, blood purification, food manufacturing more and more widely.
But because the hydrophobicity of poly (ether sulfone) film material, in the film separation process easily with material in the big molecule generation of particulate, colloidal particle or solute suction-operated, be stranded in film mutually in and cause the film pollution.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, influences the separating property and the service life of film.When being used as the bioabsorbable polymer material of human body, also be prone to bacterial infection in addition, will bring enormous economic loss and great malpractice.
At the deficiency of poly (ether sulfone) film resistance tocrocking, the researcher takes the hydrophilic modification of material and film is solved problem usually at present, as: Wu Kaifen etc. are with PES and the mixed film of SPSF, and the hydrophily of hybrid films improves, and molecular cut off diminishes; Han etc. have introduced phthalidyl on original PES molecule, form the PES-C structure, have improved the hydrophily of membrane material; Wu Kaifen, Li Shushen, Han Shijing. the research [J] of polyether sulfone-SPSF blend film. Environmental Chemistry, 1993.12 (6): 458～462. //Han S.Membranes; Membranes process[M] .New York:Plenum Press, 1986.143.But the functional polymer film that has anti-microbial property by preparation rarely has report with the research that improves its resistance tocrocking.
Summary of the invention
Technical problem to be solved by this invention provides a kind of antibacterial hollow fiber separation membrane and preparation method thereof, and prepared diffusion barrier mechanical strength is higher, has anti-damage performance preferably; Physical stability and chemical stability are better, have long service life.
A kind of antibiotic separation hollow-fibre membrane of the present invention, its component comprises: polyether sulfone, quaternary ammonium salt-acrylonitrile copolymer, pore former and organic solvent, its weight ratio are 10-30:1-10:1-20:60-90.
The inherent viscosity η of described polyether sulfone=0.3-0.7.
The inherent viscosity η of described quaternary ammonium salt-acrylonitrile copolymer=0.8-1.6.
Described pore former is selected from one or more blends in polyvinylpyrrolidone, ethylene glycol, lithium chloride, nitrate or the water.
Described organic solvent is dimethyl sulfoxide (DMSO), dimethyl formamide, dimethylacetylamide or N-methyl pyrrolidone.
The preparation method of a kind of antibiotic separation hollow-fibre membrane of the present invention comprises:
(1) preparation of casting solution
With polyether sulfone (η=0.3-0.7), quaternary ammonium salt-acrylonitrile copolymer (η=0.8-1.6), pore former, organic solvent, by weight, 10-30:1-10:1-20:60-90 mixes, and with polyether sulfone drying removal moisture, then raw material is put into dissolution kettle, at room temperature stirred swelling 0.5-1 hour earlier, be warming up to 60-100 ℃ of heating stirring and dissolving down then, time is 12-24 hour, gained solution is filtered, the deaeration purification process again;
(2) making of hollow-fibre membrane
Spinning process is to adopt dry-jet wet spinning to be shaped, at the measuring pump rotating speed is 8-20r/min, spinning pressure is under the 0.4-0.6Mpa, the spinning head that slurries are formed from two concentric tubes is extruded, after the dry-spinning path of 50-500mm, at the organic solvent weight content is that 0-20%, temperature are to solidify in 20-70 ℃ the coagulation bath to form nascent hollow-fibre membrane, nascent film drawn and washing, speed with 10-60m/min is reeled, and protects the hole and handle and be drying to obtain blend hollow fiber membrane provided by the present invention.
Described step (2) filling liquid is the aqueous solution of the aqueous solutions of organic solvent of 0-20% weight content or ethanol, glycerine system.
Described step (2) spinning head inner chamber filling liquid pressure is 1.5 * 10
-3Mpa-5.5 * 10
-3Mpa.
Described step (2) coagulation bath is the monohydric alcohol of 10-60% weight content or the aqueous solution of polyalcohol, is in order to reduce the distortion of fenestra in dry run.
The doughnut film thickness that described step (2) is spun into is 50-300 μ m, and internal diameter is 100-500 μ m, and average pore size is 0.01-0.3 μ m, 40-500L/m when pure water flux is 0.1MPa
2.h, the bovine serum albumin rejection is 30-95%, proof pressure 〉=0.1MPa.
Raw material described in the step: polyether sulfone (PES), E6020P, Shanghai Basf AG; Quaternary ammonium salt-acrylonitrile copolymer (PQA-co-AN), this laboratory self-control; Polyvinylpyrrolidone (PVP), Shanghai chemical reagents corporation, chemical pure; N-N, dimethylacetylamide (DMAC), Shang Hai Wen Min biochemical technology Co., Ltd, chemical pure.
The preparation method of described quaternary ammonium salt-acrylonitrile copolymer (PQA-co-AN) comprising:
(1) polymerizability quaternary ammonium salt monomer (PQA) is synthetic
In the three-necked bottle of the 250mL that agitator, reflux condenser and thermometer are housed, add acetone, p-chloromethyl styrene and dodecyl dimethyl tertiary amine, its weight ratio is: 30-60:3-6:4-8, under agitation being heated to acetone refluxes, get yellow emulsion behind the reaction 2h, with normal heptane product is precipitated out then, and with acetone washing 3-5 time, the product vacuum drying that leaches to constant weight, is obtained yellow powder; Reaction equation is as follows:
(2) quaternary ammonium salt-acrylonitrile copolymer (PQA-co-AN) is synthetic
In the four-hole boiling flask of the 250mL that agitator, thermometer, dropping funel and reflux condensing tube are housed, add the solvent dimethylacetylamide (DMAC) of 100mL and feed nitrogen, under agitation be warming up to 65 ℃, slowly be added drop-wise to the polymerizability quaternary ammonium salt monomer (PQA), acrylonitrile (AN) and the initiator A IBN that are dissolved in the residual solvent in the reactor, insulation polymerization 5h, the cooling cessation reaction gets the yellowish red color emulsion.With deionized water product is precipitated out then, and, the separated products vacuum drying to constant weight, is obtained the yellowish red color powder with DMAC washing three times; Reaction equation is as follows:
Used raw material in the synthetic reaction: p-chloromethyl styrene (C
9H
9Cl), chemical pure, big chemical industry Co., Ltd on the Xiangshan, Zhejiang; Dodecyl dimethyl tertiary amine (C
12H
25N (CH
3)
2), chemical pure, Shanghai Jingwei Chemical Co., Ltd.; Acetone (C
3H
6O), analyze pure, Chemical Reagent Co., Ltd., Sinopharm Group; Normal heptane (C
7H
16), analyze pure, Chinese 5-linked chemical plant, Shanghai; Acrylonitrile (AN), chemical pure is with preceding drying and heavily steaming, grand celebration Acrylic Fibers Plant; N, N-dimethylacetylamide (DMAC) are analyzed purely, and chemical reagent work is newly spilt by the Shenyang City; Azodiisobutyronitrile (AIBN), chemical pure, with preceding through ethyl alcohol recrystallization, Shishewei Chemical Co., Ltd., Shanghai.
The quaternary ammonium salt-acrylonitrile copolymer that this research is synthetic, belong to water-insoluble high molecular quaternary class antiseptic, it not only has the anti-microbial property of the slowly-releasing of high molecular quaternary group, long-acting, low toxicity, safety, and have excellent mechanical intensity and physics, chemical stability, can satisfy the needs of milipore filter and micro-filtration membrane.Utilize the antibiotic property of quaternary ammonium salt-acrylonitrile copolymer, polyether sulfone is carried out blending and modifying,, measure both and belong to the compatible system of part by methods such as glass transition temperature methods.By quaternary ammonium salt-acrylonitrile copolymer and polyethersulfone blended, and control suitable casting solution structure and forming technology condition, can prepare the blending isolation film with remarkable antibacterial properties in PSPP, different flux and different apertures.Prepared diffusion barrier mechanical strength is higher, has anti-damage performance preferably; Physical stability and chemical stability are better, have long service life.
Advantage of the present invention:
1) diffusion barrier physical stability of the present invention and chemical stability are better, and mechanical strength is higher, have anti-damage performance and long service life preferably;
(2) blending isolation film with remarkable antibacterial properties in PSPP, different flux and different apertures can be prepared by this method.
Description of drawings
Fig. 1 is the SEM figure of prepared diffusion barrier section;
Fig. 2 is the partial enlarged drawing of Fig. 1.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
Prepare burden by following component and composition: polyether sulfone 10.5%; Quaternary ammonium salt-acrylonitrile copolymer 4.5%; Polyvinylpyrrolidone 5%; Dimethylacetylamide 80%.Above-mentioned raw materials is added in the dissolution kettle, earlier at room temperature stirred swelling 1 hour, be warming up to 80 ℃ of heating stirring and dissolving down then, the time is 24 hours, again with gained solution after filtration, stand-by after the deaeration.Casting solution is spun into hollow-fibre membrane through concentric circles tubular type spinning head, and film-forming process is: measuring pump specification 0.35mL/r, and revolution speed 11r/min, air section length 180mm, inside and outside coagulating bath is a water, spinning speed 28m/min.Low temperature drying can be assembled after handle in washing, guarantor hole.Water flux is 200L/m
2.h, the rejection of bovine serum albumin is 87%, and the bacteriostasis rate of Escherichia coli, staphylococcus aureus is respectively 63% and 52%.
The SEM figure of diffusion barrier section as shown in Figure 1 and Figure 2.
Embodiment 2
Prepare burden by following component and composition: polyether sulfone 15%; Polyvinylpyrrolidone 5%; Dimethylacetylamide 80% is pressed the method dissolving system film of embodiment 1, and water flux is 280L/m
2.h, the rejection of bovine serum albumin is 37%, all is 0% to the bacteriostasis rate of Escherichia coli, staphylococcus aureus.
Claims (8)
1. antibacterial hollow fiber separation membrane, this diffusion barrier is made by following raw material:
Polyether sulfone, quaternary ammonium salt-acrylonitrile copolymer, pore former and organic solvent, its weight ratio are 10-30: 1-10: 1-20: 60-90;
The preparation method of this diffusion barrier comprises:
(1) preparation of casting solution
With polyether sulfone, quaternary ammonium salt-acrylonitrile copolymer, pore former, organic solvent, by weight, 10-30: 1-10: 1-20: 60-90 mixes, and with polyether sulfone drying removal moisture, then raw material is put into dissolution kettle, at room temperature stirred swelling 0.5-1 hour earlier, be warming up to 60-100 ℃ of heating stirring and dissolving down then, time is 12-24 hour, gained solution is filtered, deaeration purifies again;
(2) making of hollow-fibre membrane
Spinning process is to adopt dry-jet wet spinning to be shaped, and is 8-20r/min at the measuring pump rotating speed, and spinning pressure is under the 0.4-0.6MPa, and the spinning head that slurries are formed from two concentric tubes is extruded, and spinning head inner chamber filling liquid pressure is 1.5 * 10
-3MPa-5.5 * 10
-3MPa after the dry-spinning path of 50-500mm, solidifies in temperature is 20-70 ℃ coagulation bath and forms nascent hollow-fibre membrane, and nascent film drawn and washing are reeled with the speed of 10-60m/min, and protect the hole and handle and be drying to obtain antibacterial hollow fiber separation membrane; Wherein coagulation bath is the monohydric alcohol of 10-60% weight content or the aqueous solution of polyalcohol.
2. a kind of antibacterial hollow fiber separation membrane according to claim 1 is characterized in that: the inherent viscosity η of described polyether sulfone=0.3-0.7.
3. a kind of antibacterial hollow fiber separation membrane according to claim 1 is characterized in that: the inherent viscosity η of described quaternary ammonium salt-acrylonitrile copolymer=0.8-1.6.
4. antibacterial hollow fiber separation membrane according to claim 1 is characterized in that: described pore former is selected from one or more blends in polyvinylpyrrolidone, ethylene glycol, lithium chloride or the nitrate.
5. antibacterial hollow fiber separation membrane according to claim 1 is characterized in that: described organic solvent is dimethyl sulfoxide (DMSO), dimethyl formamide, dimethylacetylamide or N-methyl pyrrolidone.
6. a kind of antibacterial hollow fiber separation membrane according to claim 1 is characterized in that: described step (2) filling liquid is the aqueous solutions of organic solvent of 0-20% weight content.
7. a kind of antibacterial hollow fiber separation membrane according to claim 1 is characterized in that: the doughnut film thickness of described step (2) is 50-300 μ m, and internal diameter is 100-500 μ m, and average pore size is 0.01-0.3 μ m.
8. a kind of antibacterial hollow fiber separation membrane according to claim 1 is characterized in that: the preparation method of described quaternary ammonium salt-acrylonitrile copolymer PQA-co-AN comprises:
(1) polymerizability quaternary ammonium salt monomer PQA's is synthetic
In the three-necked bottle of the 250mL that agitator, reflux condenser and thermometer are housed, add acetone, p-chloromethyl styrene and dodecyl dimethyl tertiary amine, its weight ratio is: 30-60: 3-6: 4-8, under agitation being heated to acetone refluxes, get yellow emulsion behind the reaction 2h, with normal heptane product is precipitated out then, and with acetone washing 3-5 time, the product vacuum drying that leaches to constant weight, is obtained yellow powder; Reaction equation is as follows:
(2) quaternary ammonium salt-acrylonitrile copolymer PQA-co-AN's is synthetic
In the four-hole boiling flask of the 250mL that agitator, thermometer, dropping funel and reflux condensing tube are housed, add the solvent dimethylacetylamide DMAC of 100mL and feed nitrogen, under agitation be warming up to 65 ℃, slowly be added drop-wise to polymerizability quaternary ammonium salt monomer PQA, the acrylonitrile AN and the initator azodiisobutyronitrile AIBN that are dissolved in the residual solvent in the reactor, insulation polymerization 5h, the cooling cessation reaction gets the yellowish red color emulsion; With deionized water product is precipitated out then, and, the separated products vacuum drying to constant weight, is obtained the yellowish red color powder with DMAC washing three times; Reaction equation is as follows:
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102397760B (en) * | 2010-09-08 | 2014-04-09 | 绵阳美能材料科技有限公司 | Polyether sulfone hollow fiber ultrafiltration membrane and preparation method thereof |
| CN102688699B (en) * | 2012-05-23 | 2014-07-16 | 中国海洋大学 | Preparation method for antibacterial polyethersulfones ultrafilter membrane |
| CN102698611A (en) * | 2012-06-27 | 2012-10-03 | 上海大学 | Method for preparing polysulfone amide hollow fiber separation membrane by wet spinning |
| CN104437136A (en) * | 2014-11-04 | 2015-03-25 | 华文蔚 | Preparation method for strength-reinforced anti-microbial hollow fiber separating membrane |
| CN105727773B (en) * | 2016-03-02 | 2018-11-13 | 同济大学 | A kind of anti-bacterial and anti-fouling dyeing polymer seperation film and preparation method thereof |
| EP3431171A1 (en) * | 2017-07-19 | 2019-01-23 | Gambro Lundia AB | Filter membrane and device |
| CN110605032A (en) * | 2018-06-16 | 2019-12-24 | 苏州五颗星特种超滤膜科技有限公司 | Preparation method of finishing type hollow fiber membrane |
| CN109679834B (en) * | 2019-01-07 | 2020-06-05 | 赵涌 | Hollow fiber tube and method for in vitro large-scale production of red blood cells |
| CN111085111B (en) * | 2019-12-27 | 2022-05-17 | 天津膜天膜科技股份有限公司 | Rare earth complex acid salt antibacterial agent, antibacterial modified hollow fiber membrane and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6497868B1 (en) * | 1996-07-16 | 2002-12-24 | Toray Industries, Inc. | Graft polymer and moulded medical articles employing this |
| CN1958136A (en) * | 2006-10-17 | 2007-05-09 | 浙江大学 | Antibacterial hollow-fiber membrane, preparation method and application |
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2008
- 2008-10-24 CN CN2008102017637A patent/CN101396642B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6497868B1 (en) * | 1996-07-16 | 2002-12-24 | Toray Industries, Inc. | Graft polymer and moulded medical articles employing this |
| CN1958136A (en) * | 2006-10-17 | 2007-05-09 | 浙江大学 | Antibacterial hollow-fiber membrane, preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| Masao Senuma et al.Antibacterial acitvity of copoymers of trialkyl(4-vinylbenzyl)ammonium chlorides with acrylonitrile.《Die Angewandie Makromolekulare Chemie》.1993,第204卷11-125. * |
| Masao Senuma et al.Synthesis and Antibacterial Activity of Copolymers Having a Quaternary Ammonium Salt Side Group.《Journal of Applied Polymer Science》.1989,第37卷2837-2843. * |
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