CN102120148A - Preparation method for composite film of chitosan/sulfonated polyethersulfone and polyethersulfone and application thereof - Google Patents
Preparation method for composite film of chitosan/sulfonated polyethersulfone and polyethersulfone and application thereof Download PDFInfo
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- CN102120148A CN102120148A CN 201110020950 CN201110020950A CN102120148A CN 102120148 A CN102120148 A CN 102120148A CN 201110020950 CN201110020950 CN 201110020950 CN 201110020950 A CN201110020950 A CN 201110020950A CN 102120148 A CN102120148 A CN 102120148A
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Abstract
The invention discloses a preparation method for a composite film of chitosan/sulfonated polyethersulfone and polyethersulfone and an application thereof; the method comprises the following steps: preparing a chitosan acetic acid solution by dissolving chitosan acetic acid after deacetylation in a water solution; dissolving the polyethersulfone in a chloroform solution to prepare a polyethersulfone chloroform solution; dissolving chlorosulfonic acid in a chloroform solution to prepare into a solution, and dropwise adding the solution into the chlorosulfonic acid chloroform solution for sulfonation so as to obtain sulfonated polyethersulfone; mixing and dissolving the sulfonated polyethersulfone and the polyethersulfone in a dimethylformamide (DMF) solution to prepare a basement membrane solution, filtering, deaerating and shaving into a film to obtain a nonsymmetric basement membrane support layer in the water; and coating the chitosan solution on the basement membrane support layer to obtain the composite film through drying. The composite film has a good separating effect for separating alcohol and water. The preparation method has the advantages of simple preparation process, abundant raw materials, low cost and temperate conditions.
Description
Technical field
The present invention relates to the preparation method and the application of a kind of shitosan/sulfonated polyether sulfone-polyether sulfone composite membrane.Belong to the osmotic evaporation film separation technology field.
Background technology
The pervaporation membrane separation process has green safety, and energy consumption is low, and advantages of simple operation is described as " third generation membrane technology " and 21 century one of the most promising new and high technology.Set up the pervaporation of cover more than 100 device at present in the world, wherein most dehydrations that are used for ethanol or isopropyl alcohol.The key component that film separates is exactly a film, be used at present pervaporation alcohol moisture from film can be divided into homogeneous membrane and composite membrane two big classes.Homogeneous membrane is that main body is mixed with the homogeneous casting solution with common hydrophilic material such as polyvinyl alcohol, shitosan, hyaluronic acid, gelatin etc. promptly, handle the dry a kind of film that forms with ad hoc approach then, the homogeneous membrane mechanical performance is lower, thereby be subjected to the external force interference easily and cause the destruction of film that film can't be used, increase considerably its thickness for improving its mechanical performance, resistance in the time of can bringing separated component to see through film like this increases, and separating property descends; Therefore people utilize the higher hurricane of mechanical performance, polyether sulfone, materials such as polyacrylonitrile are done basement membrane, on basement membrane, apply the hydrophily separating layer again and form composite membrane, the separating layer of composite membrane and supporting layer play centrifugation and supporting role respectively, separating layer just can develop to reduce resistance to mass tranfer to ultra-thinization direction and increase flux like this, but because the solubility parameter of separating layer and supporting layer macromolecule member material differs bigger, the supporting layer swelling is very little or can cause peeling off between separating layer and the supporting layer when not having swelling behavior when the separating layer swelling, thereby make composite membrane lose its advantage, be difficult to long-term use.Therefore, improve the significant and application prospect of exploitation of composite membrane interface stability technology.
In recent years, the research of composite membrane interface stability has been subjected to the extensive concern of academia and industrial quarters.The method that improves interface stability mainly contains the membrane surface modification, adds adhesive layer, composite membrane integrated design etc.The membrane surface modification mainly be by graft reaction to membrane surface grafting hydrophilic high mol segment, thereby carry interface compatibility; Adhesive layer mainly is based on bionical thought, utilizes the bond properties of adhesive layer that two-layer being connected together played the effect that the buffering swelling is brought destruction, thereby improves interface stability; The composite membrane integrated design be about to hydrophilic macromolecule and hydrophobic polymer by a certain percentage mixed dissolution become the homogeneous casting solution, make it to become asymmetrical integral structure by asymmetric with the inversion of phases method, transfer micro interface between the strand to by the interface of macroscopic view, thereby improve the stability at interface.But so far, the method that increases substantially performance on the basis of raising interface stability simultaneously yet there are no report, therefore, has has originally researched and proposed a kind of design that increases substantially separating property when improving interface stability.Promptly will segregate to the nearer sulfonated polyether sulfone of shitosan solubility parameter and improve interface compatibility at the interface to improve interface stability by surface segregation and phase inversion, simultaneously because sulfonated polyether sulfone to the separating property of the effect raising shitosan of shitosan, makes the shitosan separating layer still keep considerable separation factor under thin situation.
Summary of the invention
The object of the present invention is to provide the preparation method and the application of a kind of shitosan/sulfonated polyether sulfone-polyether sulfone composite membrane.Osmotic evaporation film with the method preparation is used for separating alcohol/aqueous mixtures, shows separating effect preferably.
The present invention is achieved through the following technical solutions, the preparation method of a kind of shitosan/sulfonated polyether sulfone-polyether sulfone composite membrane, it is characterized in that comprising following process: with deacetylation be 90.2% and above shitosan to be dissolved in 60～80 ℃ of mass fractions of temperature be in 2.5% the glacial acetic acid aqueous solution, be mixed with mass concentration and be 2.5% chitosan-acetic acid solution.With mean molecule quantity is that 58000 polyether sulfone is dissolved in that to be mixed with mass concentration in the chloroformic solution be 6.3% homogeneous solution, and chlorosulfonic acid is dissolved in the chloroform, is mixed with mass concentration and is 7.4% chlorosulfonic acid chloroformic solution; In ice-water bath, 2: 1 by volume, the chlorosulfonic acid chloroformic solution is added dropwise to carries out sulfonation 1.5～6h in the polyether sulfone chloroformic solution and make sulfonated polyether sulfone, with sulfonated polyether sulfone and polyether sulfone by 1～21: 9 mass ratio mixes to be dissolved in and makes the basement membrane solution that mass concentration is 15-17% in N ' the dinethylformamide solution, basement membrane solution filters deaeration by copper mesh, scrape in glass plate immerse immediately in the deionized water asymmetric basement membrane supporting layer, to make chitosan solution then uses the spin coating instrument successively with 500r/min spin coating 10s, 1000r/min spin coating 40s, 2000r/min spin coating 20s is spun on the made basement membrane supporting layer, its coating layer thickness is 260～380 nanometers, and drying gets shitosan/sulfonated polyether sulfone-polyether sulfone composite membrane composite membrane.
Above-mentioned shitosan/the sulfonated polyether sulfone that makes-polyether sulfone composite membrane pure moisture from application, when it is used for ethanol dehydration, has separating effect preferably, at the film downstream pressure is 0.33 kPa, operating temperature is 20～80 ℃, the material liquid flow velocity is 60 liters/hour, and its separation factor is 123～453, and permeation flux is 918～1447g/ (m
2H).
The invention has the advantages that: the membrane material abundant raw material, cheap, the film preparation process is simple, mild condition.A large amount of existence of obtained membrane surface sulfonate radical make compatibility raising between basement membrane and separating layer, and the feasible separating layer anti-swelling based on shitosan of the effect of ammonia root can improve in sulfonate radical and the shitosan in addition.Prepared shitosan/sulfonated polyether sulfone-polyether sulfone composite membrane is used for ethanol dehydration, has dewatering preferably.Its separation factor is 123～453, and permeation flux is 918～1447g/ (m
2H).
Description of drawings
Fig. 1 is the section field emission electromicroscopic photograph of embodiment two prepared films
Fig. 2 is the separating layer amplification field emission electromicroscopic photograph of embodiment two prepared films
The specific embodiment
Embodiment one
Take by weighing 2.5g deacylated tRNA degree and be 90.2% shitosan, the 2.5g glacial acetic acid and the 95g aqueous solution are put into there-necked flask, put into 80 ℃ water bath with thermostatic control and heat, and stir 1h with the rotating speed of 500r/min.Shitosan all dissolves the back temperature reduces to 25 ℃, and copper mesh filters, leaves standstill the 1h deaeration, makes the chitosan-acetic acid solution of mass concentration 2.5%.Take by weighing the 10g polyether sulfone, measure the 100mL chloroformic solution and put into there-necked flask, treat that all dissolving is put into ice-water bath with there-necked flask, dropwise add the 50mL chloroformic solution that contains the 6g chlorosulfonic acid with dropping funel, rotating speed with 500r/min stirs 1.5h, obtained solution poured into repeatedly to wash in a large amount of deionized waters to solution become neutral, drying makes sulfonated polyether sulfone, take by weighing sulfonated polyether sulfone 1.2g, polyether sulfone 1.8g and 17g N ' dinethylformamide solution are put into there-necked flask, putting into 60 ℃ of waters bath with thermostatic control heats, rotating speed with 500r/min stirs 1h, reduces to room temperature, filters, leave standstill the 1h deaeration, scrape on glass plate, to immerse immediately and make asymmetric supporting layer in the deionized water.To make chitosan solution and be spun on the supporting layer, 80 ℃ of heat treatment 2h get composite membrane (film 1).The separating alcohol mass concentration is 90% the aqueous solution, and its permeation flux is 1018g/m
2.h, Dui Ying separation factor is 328.
Embodiment two
Take by weighing 2.5g deacylated tRNA degree and be 90.2% shitosan, the 2.5g glacial acetic acid and the 95g aqueous solution are put into there-necked flask, put into 80 ℃ water bath with thermostatic control and heat, and stir 1h with the rotating speed of 500r/min.Shitosan is all reduced to 25 ℃ after the dissolving, filters, leaves standstill the 1h deaeration, makes mass concentration and be 2.5% chitosan-acetic acid solution.Take by weighing the 10g polyether sulfone, measure the 100mL chloroformic solution and put into there-necked flask, treat that all dissolving is put into ice-water bath with there-necked flask, dropwise add the 50mL chloroformic solution that contains the 6g chlorosulfonic acid with dropping funel, rotating speed with 500r/min stirs 3h, solution poured into repeatedly to wash in a large amount of deionized waters to solution become neutral, drying makes sulfonated polyether sulfone, takes by weighing sulfonated polyether sulfone 1.2g, and polyether sulfone 1.8g and 17g N ' dinethylformamide solution are put into there-necked flask, putting into 60 ℃ of waters bath with thermostatic control heats, rotating speed with 500r/min stirs 1h, reduces to room temperature, filters, leave standstill the 1h deaeration, scrape on glass plate, to immerse immediately and make asymmetric supporting layer in the deionized water.To make chitosan solution and be spun on the supporting layer, 80 ℃ of heat treatment 2h get composite membrane (film 2).The separating alcohol mass concentration is 90% the aqueous solution, and its permeation flux is 1394g/m
2.h, Dui Ying separation factor is 376.
Embodiment three
Take by weighing 2.5g deacylated tRNA degree and be 90.2% shitosan, the 2.5g glacial acetic acid and the 95g aqueous solution are put into there-necked flask, put into 80 ℃ water bath with thermostatic control and heat, and stir 1h with the rotating speed of 500r/min.Shitosan is all reduced to 25 ℃ after the dissolving, filters, leaves standstill the 1h deaeration, makes mass concentration and be 2.5% chitosan-acetic acid solution.Take by weighing the 10g polyether sulfone, measure the 100mL chloroformic solution and put into there-necked flask, treat that all dissolving is put into ice-water bath with there-necked flask, dropwise add the 50mL chloroformic solution that contains the 6g chlorosulfonic acid with dropping funel, rotating speed with 500r/min stirs 4.5h, solution poured into repeatedly to wash in a large amount of deionized waters to solution become neutral, drying makes sulfonated polyether sulfone, take by weighing sulfonated polyether sulfone 1.2g, polyether sulfone 1.8g and 17g N ' dinethylformamide solution are put into there-necked flask, putting into 60 ℃ of waters bath with thermostatic control heats, rotating speed with 500r/min stirs 1h, reduces to room temperature, filters, leave standstill the 1h deaeration, scrape on glass plate, to immerse immediately and make asymmetric supporting layer in the deionized water.To make chitosan solution and be spun on the supporting layer, 80 ℃ of heat treatment 2h get composite membrane (film 3).The separating alcohol mass concentration is 90% the aqueous solution, and its permeation flux is 1135g/m
2.h, Dui Ying separation factor is 277.
Embodiment four
Take by weighing 2.5g deacylated tRNA degree and be 90.2% shitosan, the 2.5g glacial acetic acid and the 95g aqueous solution are put into there-necked flask, put into 80 ℃ water bath with thermostatic control and heat, and stir 1h with the rotating speed of 500r/min.Shitosan is all reduced to 25 ℃ after the dissolving, filters, leaves standstill the 1h deaeration, makes mass concentration and be 2.5% chitosan-acetic acid solution.Take by weighing the 10g polyether sulfone, measure the 100mL chloroformic solution and put into there-necked flask, treat that all dissolving is put into ice-water bath with there-necked flask, dropwise add the 50mL chloroformic solution that contains the 6g chlorosulfonic acid with dropping funel, rotating speed with 500r/min stirs 3h, solution poured into repeatedly to wash in a large amount of deionized waters to solution become neutral, drying makes sulfonated polyether sulfone, takes by weighing sulfonated polyether sulfone 1.2g, and polyether sulfone 1.8g and 17g N ' dinethylformamide solution are put into there-necked flask, putting into 60 ℃ of waters bath with thermostatic control heats, rotating speed with 500r/min stirs 1h, reduces to room temperature, filters, leave standstill the 1h deaeration, scrape on glass plate, to immerse immediately and make asymmetric supporting layer in the deionized water.To make chitosan solution and be spun on the supporting layer, drying at room temperature gets composite membrane (film 4).The separating alcohol mass concentration is 90% the aqueous solution, and its permeation flux is 1446g/m
2.h, Dui Ying separation factor is 124.
Embodiment five
Take by weighing 2.5g deacylated tRNA degree and be 90.2% shitosan, the 2.5g glacial acetic acid and the 95g aqueous solution are put into there-necked flask, put into 80 ℃ water bath with thermostatic control and heat, and stir 1h with the rotating speed of 500r/min.Shitosan is all reduced to 25 ℃ after the dissolving, filters, leaves standstill the 1h deaeration, makes mass concentration and be 2.5% chitosan-acetic acid solution.Take by weighing the 10g polyether sulfone, measure the 100mL chloroformic solution and put into there-necked flask, treat that all dissolving is put into ice-water bath with there-necked flask, dropwise add the 50mL chloroformic solution that contains the 6g chlorosulfonic acid with dropping funel, rotating speed with 500r/min stirs 3h, solution poured into repeatedly to wash in a large amount of deionized waters to solution become neutral, drying makes sulfonated polyether sulfone, takes by weighing sulfonated polyether sulfone 1.5g, and polyether sulfone 1.5g and 17g N ' dinethylformamide solution are put into there-necked flask, putting into 60 ℃ of waters bath with thermostatic control heats, rotating speed with 500r/min stirs 1h, reduces to room temperature, filters, leave standstill the 1h deaeration, scrape on glass plate, to immerse immediately and make asymmetric supporting layer in the deionized water.To make chitosan solution and be spun on the supporting layer, drying at room temperature gets composite membrane (film 5).The separating alcohol mass concentration is 90% the aqueous solution, and its permeation flux is 1117g/m
2.h, Dui Ying separation factor is 300.
Embodiment six
Take by weighing 2.5g deacylated tRNA degree and be 90.2% shitosan, the 2.5g glacial acetic acid and the 95g aqueous solution are put into there-necked flask, put into 80 ℃ water bath with thermostatic control and heat, and stir 1h with the rotating speed of 500r/min.Shitosan is all reduced to 25 ℃ after the dissolving, filters, leaves standstill the 1h deaeration, makes the chitosan-acetic acid solution of mass concentration 2.5%.Take by weighing the 10g polyether sulfone, measure the 100mL chloroformic solution and put into there-necked flask, treat that all dissolving is put into ice-water bath with there-necked flask, dropwise add the 50mL chloroformic solution that contains the 6g chlorosulfonic acid with dropping funel, rotating speed with 500r/min stirs 3h, solution poured into repeatedly to wash in a large amount of deionized waters to solution be neutral, drying makes sulfonated polyether sulfone, takes by weighing sulfonated polyether sulfone 1.8g, and polyether sulfone 1.2g and 17g N ' dinethylformamide solution are put into there-necked flask, putting into 60 ℃ of waters bath with thermostatic control heats, rotating speed with 500r/min stirs 1h, reduces to room temperature, filters, leave standstill the 1h deaeration, scrape on glass plate, to immerse immediately and make asymmetric supporting layer in the deionized water.To make chitosan solution and be spun on the supporting layer, drying at room temperature gets composite membrane (film 6).The separating alcohol mass concentration is 90% the aqueous solution, and its permeation flux is 918g/m
2.h, Dui Ying separation factor is 291.
Comparative Examples one
Take by weighing 2.5g deacylated tRNA degree and be 90.2% shitosan, the 2.5g glacial acetic acid and the 95g aqueous solution are put into there-necked flask, put into 80 ℃ water bath with thermostatic control and heat, and stir 1h with the rotating speed of 500r/min.Shitosan is all reduced to 25 ℃ after the dissolving, filters, leaves standstill the 1h deaeration, makes mass concentration and be 2.5% chitosan-acetic acid solution.Take by weighing polyether sulfone 3g and 17g N ' dinethylformamide solution is put into there-necked flask, put into 60 ℃ of waters bath with thermostatic control and heat, stir 1h with the rotating speed of 500r/min, reduce to room temperature, the 1h deaeration is left standstill in filtration, scrapes to immerse immediately on glass plate to make asymmetric supporting layer in the deionized water.To make chitosan solution and be spun on the supporting layer, 80 ℃ of heat treatment 2h get composite membrane (film 7).The separating alcohol mass concentration is 90% the aqueous solution, and its permeation flux is 1406g/m
2.h, Dui Ying separation factor is 50.
Claims (2)
1. the preparation method of shitosan/sulfonated polyether sulfone-polyether sulfone composite membrane, it is characterized in that comprising following process: with deacetylation be 90.2% and above shitosan to be dissolved in 60～80 ℃ of mass fractions of temperature be in 2.5% the glacial acetic acid aqueous solution, be mixed with mass concentration and be 2.5% chitosan-acetic acid solution; With mean molecule quantity is that 58000 polyether sulfone is dissolved in that to be mixed with mass concentration in the chloroformic solution be 6.3% homogeneous solution, and chlorosulfonic acid is dissolved in the chloroform, is mixed with mass concentration and is 7.4% chlorosulfonic acid chloroformic solution; In ice-water bath, 2: 1 by volume, the chlorosulfonic acid chloroformic solution is added dropwise to carries out sulfonation 1.5～6h in the polyether sulfone chloroformic solution and make sulfonated polyether sulfone, with sulfonated polyether sulfone and polyether sulfone by 1～21: 9 mass ratio mixes to be dissolved in and makes the basement membrane solution that mass concentration is 15-17% in N ' the dinethylformamide solution, basement membrane solution filters deaeration by copper mesh, scrape in glass plate immerse immediately in the deionized water asymmetric basement membrane supporting layer, to make chitosan solution then uses the spin coating instrument successively with 500r/min spin coating 10s, 1000r/min spin coating 40s, 2000r/min spin coating 20s is spun on the made basement membrane supporting layer, its coating layer thickness is 260～380 nanometers, and drying gets shitosan/sulfonated polyether sulfone-polyether sulfone composite membrane composite membrane.
2. the application of the shitosan/sulfonated polyether sulfone that makes by the described method of claim 1-polyether sulfone composite membrane, be used for pure moisture from, at the film downstream pressure is 0.33KPa, operating temperature is 20～80 ℃, the material liquid flow velocity is 60 liters/hour, separation factor is 123～453, and permeation flux is 918～1447g/ (m
2H).
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103252177A (en) * | 2013-05-14 | 2013-08-21 | 浙江大学 | Glycosyl/sulfonated modified affiliative polymer hollow fiber separating membrane, and preparation method and use thereof |
| CN106823841A (en) * | 2017-01-18 | 2017-06-13 | 燕山大学 | A kind of preparation method of polyether sulfone function and service seperation film |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1413761A (en) * | 2002-09-17 | 2003-04-30 | 天津大学 | Preparation method of affinity polysulfone-chitosan compound asymmetrical ultrafiltration film |
| WO2005007277A1 (en) * | 2003-07-18 | 2005-01-27 | UNIVERSITé LAVAL | Solvent resistant asymmetric integrally skinned membranes |
| CN1730141A (en) * | 2005-08-04 | 2006-02-08 | 浙江大学 | Process for preparing co-mixed polyethersulfone platform complex film |
| CN101039744A (en) * | 2004-08-13 | 2007-09-19 | 麦克马斯特大学 | Composite material comprising a non-crosslinked gel polymer |
| US7638235B2 (en) * | 2006-09-22 | 2009-12-29 | Gm Global Technology Operations, Inc. | Internal proton exchange membrane humidification and cooling with automotive coolant |
-
2011
- 2011-01-19 CN CN 201110020950 patent/CN102120148B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1413761A (en) * | 2002-09-17 | 2003-04-30 | 天津大学 | Preparation method of affinity polysulfone-chitosan compound asymmetrical ultrafiltration film |
| WO2005007277A1 (en) * | 2003-07-18 | 2005-01-27 | UNIVERSITé LAVAL | Solvent resistant asymmetric integrally skinned membranes |
| CN101039744A (en) * | 2004-08-13 | 2007-09-19 | 麦克马斯特大学 | Composite material comprising a non-crosslinked gel polymer |
| CN1730141A (en) * | 2005-08-04 | 2006-02-08 | 浙江大学 | Process for preparing co-mixed polyethersulfone platform complex film |
| US7638235B2 (en) * | 2006-09-22 | 2009-12-29 | Gm Global Technology Operations, Inc. | Internal proton exchange membrane humidification and cooling with automotive coolant |
Cited By (17)
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| CN103252177A (en) * | 2013-05-14 | 2013-08-21 | 浙江大学 | Glycosyl/sulfonated modified affiliative polymer hollow fiber separating membrane, and preparation method and use thereof |
| CN109689887A (en) * | 2016-07-08 | 2019-04-26 | 加州理工学院 | For carrying out the method and apparatus for flowing through capture of analytes in low concentration |
| CN106823841A (en) * | 2017-01-18 | 2017-06-13 | 燕山大学 | A kind of preparation method of polyether sulfone function and service seperation film |
| CN106823841B (en) * | 2017-01-18 | 2019-08-23 | 燕山大学 | A kind of preparation method of polyether sulfone function and service seperation film |
| CN108295677B (en) * | 2018-04-11 | 2019-06-11 | 山东科技大学 | A kind of modification of chitosan/sulfonated polyether sulfone cation-exchange membrane and preparation method thereof |
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| CN102120148B (en) | 2013-05-29 |
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