CN1194801C - Preparation method of nanometer Al2O3Sio2 polysulfone composite film having intermediate phase structure - Google Patents
Preparation method of nanometer Al2O3Sio2 polysulfone composite film having intermediate phase structure Download PDFInfo
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- CN1194801C CN1194801C CNB031303773A CN03130377A CN1194801C CN 1194801 C CN1194801 C CN 1194801C CN B031303773 A CNB031303773 A CN B031303773A CN 03130377 A CN03130377 A CN 03130377A CN 1194801 C CN1194801 C CN 1194801C
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Abstract
The present invention discloses a method for preparing a composite membrane with middle phase structure by uniformly dispersing fine nanometer powders of Al2O3. SiO2 compounds into polysulphone, which belongs to the technology of preparing a composite membrane. The method comprises: nanometer composite metal oxide and polysulphone are used as raw materials, and the composite membrane with middle phase structure is prepared by the processes of polysulphone dissolution, pretreatment and dispersion of the nanometer metal oxide, mixing of polysulphone sol and solution of nanometer composite metal oxide, molding and film-forming of middle phases, solvent leaching and member post-treatment. The method has the advantages that fine nanometer powders of composite metal oxide Al2O3. SiO2 with high surface acidity and strong hydrophilicity are uniformly dispersed in polysulphone to prepare composite membrane material with middle phase structure between the polysulphone and the nanometer Al2O3. SiO2. The composite membrane has the advantages of simple preparing technology, convenient operation, compaction resistance, high intensity, favorable toughness, high flux, pollution resistance, high temperature resistance, easy cleaning, low production cost, etc.
Description
Technical field
The present invention relates to a kind of with nanometer Al
2SiO
5The compound fine powder evenly spreads to the method for preparing the composite membrane with middle phase structure in the polysulfones.The technology of preparing that belongs to composite membrane.
Background technology
Along with the raising of development of modern industry and living standards of the people, all to give off a large amount of oil-containings and the waste water of organic pollution.The oil and the organic pollution that adopt usual way particle diameter can not be lower than 30 μ m are removed effectively.Therefore must carry out the standard that advanced treating can reach discharging and reuse to these waste water.Membrane separation technique is that oil-containing and organic matter sewage are carried out the feasible of advanced treating and effective method.When membrane separation process was handled oil-containing and organic pollution sewage, film was subject to pollutions such as oil, and the film surface forms gel layer, even also can cause the obstruction of fenestra.Handle the organic film of film and the inoranic membrane of such sewage at present.Organic film preparation technology is simple, and membrane material is wide in variety, modification easily, and pliability is good, and low price can be made into various forms of membrane modules.But organic film has non-refractory, pH value narrow application range, and pore-size distribution is wide, and mechanical strength is low, and permeability is low, shortcomings such as easy hydrolysis.Along with the development of material science, inoranic membrane grows up as a new and high technology in recent decades.Advantage such as inoranic membrane has high temperature resistant, anti-strong acid, highly basic and organic solvent, anti-microbial attack, mechanical strength height, pore-size distribution are narrow, but also exist filming technology complexity (calcining), the poor reproducibility of film, preparation small-bore film difficulty, the crisp pliability of matter is poor, shortcomings such as cost height.Therefore, develop the composite membrane that has organic film and inoranic membrane two-fold advantage concurrently and become one of exploitation focus of present film separation field.Existing at present with ZrO
2, Al
2O
3And SiO
2The micron fine powder is distributed in polysulfones, polypropylene, cellulose acetate and the polyamide research with hydrophilic, the withstand voltage real performance of improving organic polymer films.Processes such as the dispersion of the pre-treatment, metal oxide that the preparation technology of such composite membrane comprises polymer dissolution, metallic oxide fine powder in polymer solution, film forming, solvent leaching.The composite membrane of making is owing to adopt micron-sized metal oxide microparticle, causes that adhesion toughness weak, film is relatively poor between particulate and the polymer, pore-size distribution is uneven, the performance of film is low, range of application is narrow.Moreover the metal oxide of employing mostly is one pack system, and poor, the hydrophilic ability of surface acidity is low, and undesirable with the composite membrane hydrophily that mixed with polymers is made, the anti-pollution ability is low.When being used for oil-containing and organic matter sewage disposal, its performance is not ideal enough.
Summary of the invention
The object of the present invention is to provide a kind of nanometer Al with middle phase structure
2SiO
5The preparation method of-polysulfone composite membrane.It is simple, easy to operate that this method has preparation technology, with the composite membrane of this method preparation have withstand voltage real, intensity is high, good toughness, flux height, anti-pollution, high temperature resistant, easy cleaning and the low characteristics of production cost.
For achieving the above object, the present invention is realized by following technical proposals.To comprise that nano composite metal oxide and polysulfones are raw material, through the mixing that comprising polysulfones dissolving, nano-metal-oxide pre-treatment and dispersion, polysulfones colloidal sol and nano composite metal oxide solution, middle mutually formation and film forming, solvent leach and the method for the composite membrane with middle phase structure of the last handling process preparation of film, it is characterized in that comprising following concrete steps:
1, polysulfones and solvent are dissolved in dimethyl formamide, dimethylacetylamide or the N-N-methyl-2-2-pyrrolidone N-by mass ratio 1～5, then by polysulfones and pore-foaming agent mass ratio 0.2～0.5, pore-foaming agent polyvinylpyrrolidone, polyethylene glycol, acetone or chloroform are added in the above-mentioned polysulfones solution, stir 4～15h down in 20～65 ℃;
2, with nanometer Al
2SiO
5With surfactant silane, titanate esters, stearic acid or organosilicon, be 0.2～0.8 in 18～30 ℃ of 8～48h that reflux by mass ratio, carry out surface treatment;
3, the nanometer Al that step 2 is handled
2SiO
5Be dispersed in solvent dimethyl formamide or dimethylacetylamide or the N-N-methyl-2-2-pyrrolidone N-, solvent load is nanometer Al
2SiO
5With the mass ratio of solvent be 0.5～3,10～30min then vibrates in ultrasonic machine;
4, the nanometer Al that step 3 is prepared
2SiO
5Solution adds in the prepared polysulfones colloidal sol of step 1 and mixes, at control nanometer Al
2SiO
5With the mass ratio of polysulfones is to obtain making film sol liquid after evenly mixing deaeration 20～30h under 0.1～0.5 condition;
5, step 4 system film sol liquid is applied or hollow spray silk film forming through flat board; Obtain nanometer Al through the alcohol solution processing procedure again
2SiO
5-polysulfone composite membrane.
Above-mentioned nano composite metal oxide Al
2SiO
5Particle diameter be 1～200nm.
Above-mentioned dissolving polysulfones solvent is dimethyl formamide, dimethylacetylamide.
Above-mentioned pore-foaming agent is polyvinylpyrrolidone and chloroform.
Above-mentioned surfactant silane is poly-diethylsilane and poly dimethyl silane; Stearic acid is an odium stearate.
The invention has the advantages that surface acidity is strong, that hydrophily is strong composite metal oxide Al
2SiO
5The nanoscale fine powder evenly spreads in the polysulfones, prepares at polysulfones and nanometer Al
2SiO
5Between have middle phase structure composite film material.This composite membrane have preparation technology simple, easy to operate, withstand voltage real, intensity is high, good toughness, flux height, anti-pollution, high temperature resistant, easy cleaning and production cost are low etc.
The specific embodiment
Embodiment one: under 30 ℃ be 40000 polysulfones dissolving 10h with the 50g molecular weight in 100g dimethyl formamide and 1g chloroform soln; With the 5g granularity is the Al of 45nm
2SiO
5Gather diethylsilane in 20 ℃ of backflow 24h with 20g; Filtration is placed on ultrasonic machine vibration 10min in the 10g dimethyl formamide; With polysulfones solution and Al
2SiO
5Solution mixing deaeration 24h; Glue is made the hollow-fibre membrane of external diameter 100 μ m, internal diameter 30 μ m; Film is soaked 2min with 10% ethanol water; Glycerine water solution with 35% soaks behind the 20min film air-dry.The porosity of film is 71% after tested, and molecular cut off is 30000～80000, and water flux is 107L/m
2H.
Embodiment two: at 300g dimethylacetylamide and 60g molecular weight is under 45 ℃ to be 40000 polysulfones dissolving 8h with the 100g molecular weight in 450 the polyglycol solution; With the 20g granularity is the Al of 85nm
2SiO
5With the 40g odium stearate in 30 ℃ of backflow 12h; Filtration is placed on ultrasonic machine vibration 25min in the 40g dimethylacetylamide; With polysulfones solution and Al
2SiO
5Solution mixing deaeration 20h; Glue is made the hollow-fibre membrane of external diameter 200 μ m, internal diameter 40 μ m; Film is soaked 5min with 5% methanol aqueous solution; Glycerine water solution with 50% soaks behind the 15min film air-dry.The porosity of film is 77% after tested, and molecular cut off is 3000～95000, and water flux is 112L/m
2H.
Embodiment three: under 25 ℃ be 40000 polysulfones dissolving 15h with the 80g molecular weight in 80gN-N-methyl-2-2-pyrrolidone N-and 16g acetone soln; With the 24g granularity is the Al of 135nm
2SiO
5With 120g poly dimethyl silane in 25 ℃ of backflow 30h; Filtration is placed on ultrasonic machine vibration 15min in the 8gN-N-methyl-2-2-pyrrolidone N-; With polysulfones solution and Al
2SiO
5Solution mixing deaeration 24h; Glue is made the hollow-fibre membrane of external diameter 200 μ m, internal diameter 35 μ m; Film is soaked 2min with 15% aqueous propanol solution; Glycerine water solution with 55% soaks behind the 30min film air-dry.The porosity of film is 67% after tested, and molecular cut off is 2000～15000, and water flux is 109L/m
2H.
Claims (5)
1, a kind of nanometer Al with middle phase structure
2SiO
5The preparation method of-polysulfone composite membrane, this method is to comprise that nano composite metal oxide and polysulfones are raw material, through the mixing that comprising polysulfones dissolving, nano-metal-oxide pre-treatment and dispersion, polysulfones colloidal sol and nano composite metal oxide solution, middle mutually formation and film forming, solvent leach and the composite membrane with middle phase structure of the last handling process preparation of film, it is characterized in that comprising following concrete steps:
1) polysulfones and solvent are dissolved in dimethyl formamide, dimethylacetylamide or the N-N-methyl-2-2-pyrrolidone N-by mass ratio 1～5, then by polysulfones and pore-foaming agent mass ratio 0.2～0.5, pore-foaming agent polyvinylpyrrolidone, polyethylene glycol, acetone or chloroform are added in the above-mentioned polysulfones solution, stir 4～15h down in 20～65 ℃;
2) with nanometer Al
2SiO
5With surfactant silane, titanate esters, stearic acid or organosilicon, be 0.2～0.8 in 18～30 ℃ of 8～48h that reflux by mass ratio, carry out surface treatment;
3) with step 2) the nanometer Al that handles
2SiO
5Be dispersed in solvent dimethyl formamide or dimethylacetylamide or the N-N-methyl-2-2-pyrrolidone N-, solvent load is nanometer Al
2SiO
5With the mass ratio of solvent be 0.5～3,10～30min then vibrates in ultrasonic machine;
4) the nanometer Al that step 3) is prepared
2SiO
5Solution adds in the prepared polysulfones colloidal sol of step 1) and mixes, at control nanometer Al
2SiO
5With the mass ratio of polysulfones is to obtain making film sol liquid after evenly mixing deaeration 20～30h under 0.1～0.5 condition;
5) step 4) system film sol liquid is applied or hollow spray silk film forming through flat board; Obtain nanometer Al through the alcohol solution processing procedure again
2SiO
5-polysulfone composite membrane.
2, by the described nanometer Al of claim 1 with middle phase structure
2SiO
5The preparation method of-polysulfone composite membrane is characterized in that: nano composite metal oxide Al
2SiO
5Particle diameter be 1～200nm.
3, by the described nanometer Al of claim 1 with middle phase structure
2SiO
5The preparation method of-polysulfone composite membrane is characterized in that: the solvent of dissolving polysulfones is dimethyl formamide, dimethylacetylamide.
4, by the described nanometer Al of claim 1 with middle phase structure
2SiO
5The preparation method of-polysulfone composite membrane is characterized in that: pore-foaming agent is polyvinylpyrrolidone and chloroform.
5, by the described nanometer Al of claim 1 with middle phase structure
2SiO
5The preparation method of-polysulfone composite membrane is characterized in that: the silane of surfactant is poly-diethylsilane and poly dimethyl silane; Stearic acid is an odium stearate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031303773A CN1194801C (en) | 2003-07-09 | 2003-07-09 | Preparation method of nanometer Al2O3Sio2 polysulfone composite film having intermediate phase structure |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031303773A CN1194801C (en) | 2003-07-09 | 2003-07-09 | Preparation method of nanometer Al2O3Sio2 polysulfone composite film having intermediate phase structure |
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| Publication Number | Publication Date |
|---|---|
| CN1478590A CN1478590A (en) | 2004-03-03 |
| CN1194801C true CN1194801C (en) | 2005-03-30 |
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| CNB031303773A Expired - Fee Related CN1194801C (en) | 2003-07-09 | 2003-07-09 | Preparation method of nanometer Al2O3Sio2 polysulfone composite film having intermediate phase structure |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1305553C (en) * | 2005-06-22 | 2007-03-21 | 南京工业大学 | Method for preparing organic-inorganic composite membrane by self-assembly technology |
| CN102512996B (en) * | 2011-12-09 | 2014-06-11 | 浙江工业大学 | Silica nanoparticle blended modified polysulfone membrane and preparation method thereof |
| CN102600740A (en) * | 2012-03-27 | 2012-07-25 | 东华大学 | Preparation method of Mullite-polyethersulfone hybrid separation membrane with high sol content |
| CN105817147B (en) * | 2016-04-28 | 2017-12-29 | 湖南尔康制药股份有限公司 | It is a kind of to be used to refine modified polysulfone film of propane diols and preparation method thereof |
| CN109289558A (en) * | 2018-11-26 | 2019-02-01 | 暨南大学 | A kind of nanometer alumina modified polysulfone ultrafiltration membrane and preparation method thereof |
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2003
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