CN1164353C - Process for preparing polyurethane/acetyl cellulose blend micro-porous filter membrane - Google Patents
Process for preparing polyurethane/acetyl cellulose blend micro-porous filter membrane Download PDFInfo
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- CN1164353C CN1164353C CNB01110077XA CN01110077A CN1164353C CN 1164353 C CN1164353 C CN 1164353C CN B01110077X A CNB01110077X A CN B01110077XA CN 01110077 A CN01110077 A CN 01110077A CN 1164353 C CN1164353 C CN 1164353C
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- polyurethane
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- dimethyl formamide
- acetyl cellulose
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Abstract
The present invention uses the crossblend of polyurethane and cellulose acetate to prepare a membrane. The membrane has favorable hydrophilicity and biocompatibility. The membrane comprises more terminal amino groups which are suitable for affinity and modification, so that the membrane is used as a basal membrane of an affinity membrane. The structure of the prepared membrane is a decorticate spongy structure with slight asymmetry. The membrane has the aperture of 0.3 to 2 mum and the porosity of 70 to 85. The content of the terminal amino groups is 61.6 mu mol per gram of membrane. Under the pressure of 0.05MPa, the pure water penetration amount is 25 ml/min.cm<2>.
Description
The invention belongs to a kind of preparation method of polyurethane/acetyl cellulose blend micro-porous filter membrane.
Micro-filtration membrane with the polyurethane/acetyl cellulose blend preparation has good hydrophilicity and biocompatibility, contains the terminal amino group of more amount, is suitable for affine modification, as the basement membrane of affinity membrane.People such as Sivakumar (POLYMER INTERNATIONAL 1998, Vol 47, Iss 3, pp311-316) miscible with cellulose acetate and polyurethane in polar solvent, make milipore filter, its aperture is less than 0.1 μ m, characterize with pure water flux, compactibility and ESEM, the PVP addition is discussed in research, and the composition of polymer is to the influence of film properties, and is used for the separation that albumen and GOLD FROM PLATING SOLUTION belong to ion; U.S. Pat Pat.6013340 then is with polyurethane system gas separation membrane; (JOURNAL OF MEMBRANE SCIENCE 1992, Vol 74, are basement membrane with nylon (polycaprolactam) micropore pp115-129), and it is carried out modification, are used for the affine adsorption process of medical treatment for K.Kugel etc.
The weak point of these technology is application (only limiting to ultrafiltration separates with gas) that blend film does not have the micro-filtration scope, and the aperture is less, is lower than 0.1 μ m; Therefore and the nylon membrane terminal amino group content is generally lower, is 20 μ mol/g films, and needing hydrolysis or reacting with lysine increases amino content, and the former can reduce film strength, and the latter then effect is little, and nylon membrane has strong non-specific adsorption to protein.
The preparation method who the purpose of this invention is to provide a kind of polyurethane/acetyl cellulose blend micro-porous filter membrane, this preparation method's advantage is easy and simple to handle, can make the micro-filtration membrane that the aperture is 0.3-2 μ m, introduce a large amount of terminal amino groups and strengthen film strength by the polyurethane of blend simultaneously.
For achieving the above object, the technical solution used in the present invention is:
Get polyurethane with the polymerization in dimethyl formamide and acetone mixed solvent of methyl diphenylene diisocyanate, polyethylene glycol, ethylenediamine.With cellulose diacetate and polyurethane is membrane material, be dissolved in dimethyl formamide and acetone mixed solvent, with water and polyalcohols is non-solvent, the preparation preparation liquid, on glass plate, moisture absorption precipitates in air with film liquid blade coating, treat to immerse in the water after phase-splitting is finished substantially, make exchange of solvent fully and remove unnecessary component, the cured film structure promptly makes dull and stereotyped micro-filtration membrane to do wet method.
Specifically, in above-mentioned preparation method, select methyl diphenylene diisocyanate, polyethylene glycol (molecular weight 1000-5000), ethylenediamine, its mol ratio are 2: 1: 2-8: 5: 7, polymerization got polyurethane in 35-60% dimethyl formamide and 25-40% acetone mixed solvent.With the degree of polymerization of the different proportionings (percentage by weight 4: 1 to 1: 1) of dimethyl formamide and acetone control polyurethane, be chain extender with the ethylenediamine, make gained polyurethane contain a large amount of terminal amino groups; Membrane material is with polyurethane/acetyl cellulose blend, content is the cellulose diacetate of weight ratio 5-15% in the film liquid, the polyurethane of 0.5%-3%, solvent is dimethyl formamide and acetone mixed solvent, content is dimethyl formamide 35-60%, and acetone 25-40% is a non-solvent with water and polyalcohols, water is 0-15%, polyalcohols 0-15%; On glass plate, thick 400-500 μ m is in 30-80 ℃ with film liquid blade coating, solvent evaporates and moisture absorption precipitation 15-30min in the air of relative humidity 50-90%, the film that phase-splitting is finished substantially immerses 24h in the water, makes exchange of solvent fully and remove unnecessary component, cured film structure.
In above-mentioned preparation method, by telomerized polymer concentration, DMF and content of acetone are regulated the viscosity of preparation liquid, control solvent, non-solvent diffusion velocity, and by telomerized polymer, solvent, the content of non-solvent in preparation liquid, aperture and structure that the temperature and humidity of control film forming is come controlling diaphragm, can obtain membrane aperture is 0.3-2 μ m, porosity is 70-85%, terminal amino group content is 61.6 μ mol/g micro-filtration membrane, and cellulose acetate and polyurethane have good blood compatibility, can be used for the blood purification process.
Below in conjunction with embodiment the present invention is elaborated:
Embodiment 1, with methyl diphenylene diisocyanate, polyethylene glycol (molecular weight 1000), ethylenediamine, its mol ratio is 2: 1: 1, polymerization in percentage by weight 60% dimethyl formamide and 40% acetone mixed solvent, with the cellulose diacetate of percentage by weight 15%, 3% polyurethane, dimethyl formamide 35%, acetone 40%, water 0%, glycerine 15%, preparation preparation liquid, with film liquid blade coating on glass plate, thick 500 μ m, in 80 ℃, moisture absorption precipitation 30min in the air of relative humidity 90%, treat to immerse in the water after phase-splitting is finished substantially, make exchange of solvent fully and remove unnecessary component, the cured film structure makes dull and stereotyped micro-filtration membrane.
Embodiment 2, with methyl diphenylene diisocyanate, polyethylene glycol (molecular weight 3000), ethylenediamine, its mol ratio is 8: 3: 5, polymerization in percentage by weight 80% dimethyl formamide and 20% acetone mixed solvent, with the cellulose diacetate of percentage by weight 5%, 0.5% polyurethane, dimethyl formamide 47%, acetone 25%, water 0%, ethylene glycol 15%, preparation preparation liquid, with film liquid blade coating on glass plate, thick 400 μ m, in 30 ℃, moisture absorption precipitation 15min in the air of relative humidity 50%.All the other conditions are with embodiment 1.
Embodiment 3, with methyl diphenylene diisocyanate, polyethylene glycol (molecular weight 5000), ethylenediamine, its mol ratio is 8: 5: 7, polymerization in percentage by weight 50% dimethyl formamide and 50% acetone mixed solvent, with the cellulose diacetate of percentage by weight 10%, 1.5% polyurethane, dimethyl formamide 60%, acetone 32%, water 8%, glycerine 8%, preparation preparation liquid, with film liquid blade coating on glass plate, thick 450 μ m, in 55 ℃, moisture absorption precipitation 22min in the air of relative humidity 70%.All the other conditions are with embodiment 1.
The made membrane structure of the present invention is with polyurethane/acetyl cellulose blend system film, have good hydrophilicity and biocompatibility, contain the terminal amino group of more amount, be suitable for affine modification, basement membrane as affinity membrane, made membrane structure is decorticate spongelike structure, has slight asymmetricly, and membrane aperture is 0.3-2 μ m, porosity is 70-85%, terminal amino group content is 61.6 μ mol/g films, and at 0.05MPa, pure water flux is 25ml/mincm
2
Claims (6)
1. polyurethane/acetyl cellulose blend micro-porous filter membrane preparation method is characterized in that:
Get polyurethane with the polymerization in dimethyl formamide and acetone mixed solvent of methyl diphenylene diisocyanate, polyethylene glycol, ethylenediamine, with cellulose diacetate and polyurethane is membrane material, be dissolved in dimethyl formamide and acetone mixed solvent, with water and/or polyalcohols is non-solvent, the preparation preparation liquid, with film liquid blade coating on glass plate, moisture absorption precipitation in air, treat to immerse in the water after phase-splitting is finished substantially, make exchange of solvent fully and remove unnecessary component, the cured film structure promptly makes dull and stereotyped micro-filtration membrane to do wet method.
2, a kind of polyurethane/acetyl cellulose blend micro-porous filter membrane preparation method according to claim 1, it is characterized in that described polyurethane is: methyl diphenylene diisocyanate, polyethylene glycol, ethylenediamine, its mol ratio is 2: 1: 1-8: 5: 7, polymerization makes in dimethyl formamide and acetone mixed solvent, controls the degree of polymerization of polyurethane with the different proportionings of dimethyl formamide and acetone.
3, a kind of polyurethane/acetyl cellulose blend micro-porous filter membrane preparation method according to claim 1, it is characterized in that described membrane material is with polyurethane/acetyl cellulose blend, the content cellulose diacetate of 5-15% that is weight percentage in the film liquid, the polyurethane of 0.5%-3%, solvent is dimethyl formamide and acetone mixed solvent, content is weight percentage, and polymerization gets polyurethane in 35-60% dimethyl formamide and the 25-40% acetone mixed solvent, with water and/or polyalcohols is non-solvent, water is 0-15%, polyalcohols 0-15%.
4, a kind of polyurethane/acetyl cellulose blend micro-porous filter membrane preparation method according to claim 1, it is characterized in that described dried wet method system film, with film liquid blade coating on glass plate, thick 400-500 μ m, in 30-80 ℃, solvent evaporates and moisture absorption precipitation 15-30min in the air of relative humidity 50-90%, the film that phase-splitting is finished substantially immerses 24h in the water, make exchange of solvent fully and remove unnecessary component, cured film structure.
5, a kind of polyurethane/acetyl cellulose blend micro-porous filter membrane preparation method according to claim 2 is characterized in that described molecular weight polyethylene glycol is 1000-5000.
6, a kind of polyurethane/acetyl cellulose blend micro-porous filter membrane preparation method according to claim 1, the percentage by weight that it is characterized in that described dimethyl formamide and acetone mixed solvent is 4: 1 to 1: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB01110077XA CN1164353C (en) | 2001-03-29 | 2001-03-29 | Process for preparing polyurethane/acetyl cellulose blend micro-porous filter membrane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB01110077XA CN1164353C (en) | 2001-03-29 | 2001-03-29 | Process for preparing polyurethane/acetyl cellulose blend micro-porous filter membrane |
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| Publication Number | Publication Date |
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| CN1377727A CN1377727A (en) | 2002-11-06 |
| CN1164353C true CN1164353C (en) | 2004-09-01 |
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| CNB01110077XA Expired - Fee Related CN1164353C (en) | 2001-03-29 | 2001-03-29 | Process for preparing polyurethane/acetyl cellulose blend micro-porous filter membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106390591A (en) * | 2016-09-26 | 2017-02-15 | 海信集团有限公司 | Filtering sponge and preparation thereof, filtering device and laser projection equipment |
| DE102017112492A1 (en) * | 2017-06-07 | 2018-12-13 | Alexander Ott | Microfiltration membrane, fumigation membrane and use of films of polymeric material |
| CN112743943B (en) * | 2020-12-30 | 2023-09-26 | 上海海洋大学 | Controlled release type degradable active packaging film and preparation method and application thereof |
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