CN102120148B - 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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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 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 advantage easy and simple to handle is described as " third generation membrane technology " and 21 century one of the most promising new and high technology.At present in the world built vertical more than 100 cover pervaporation device, wherein most dehydrations that are used for ethanol or isopropyl alcohol.The key component that film separates is exactly film, be used at present pervaporation alcohol moisture from film can be divided into homogeneous membrane and composite membrane two large classes.Homogeneous membrane namely is mixed with the homogeneous casting solution take common hydrophilic material such as polyvinyl alcohol, shitosan, hyaluronic acid, gelatin etc. as main body, then process the dry a kind of film that forms with ad hoc approach, the homogeneous membrane mechanical performance is lower, thereby be subjected to 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 increment in the time of can bringing so separated component to see through film, separating property descends; Therefore people utilize the higher hurricane of mechanical performance, polyether sulfone, the materials such as polyacrylonitrile are done basement membrane, apply the hydrophily separating layer at basement membrane again and form composite membrane, the separating layer of composite membrane and supporting layer play respectively centrifugation and supporting role, separating layer just can increase flux to reduce resistance to mass tranfer to the ultrathin future development like this, but because the solubility parameter of separating layer and supporting layer macromolecule member material differs larger, 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 subject 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 simultaneously performance on the basis of raising interface stability 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.Namely will segregate to the nearer sulfonated polyether sulfone of shitosan solubility parameter by surface segregation and phase inversion and improve at the interface interface compatibility to improve interface stability, 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 in thinner situation.
Summary of the invention
The object of the present invention is to provide preparation method and the application of a kind of shitosan/sulfonated polyether sulfone-polyether sulfone composite membrane.Osmotic evaporation film with the method preparation for separating of ethanol/water mixture, shows preferably separating effect.
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.Be that 58000 polyether sulfone is dissolved in that to be mixed with mass concentration in the chloroformic solution be 6.3% homogeneous solution with mean molecule quantity, chlorosulfonic acid is dissolved in the chloroform, be mixed with mass concentration and be 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 and immerse immediately in the deionized water to get asymmetric basement membrane supporting layer, then use the spin coating instrument successively with 500r/min spin coating 10s chitosan solution processed, 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 preferably separating effect, it is 0.33 kPa at the film downstream pressure, operating temperature is 20～80 ℃, the material liquid flow velocity is 60 l/hs, 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 between basement membrane and separating layer compatibility improve, in addition in sulfonate radical and the shitosan effect of ammonia root so that take shitosan as main separating layer swelling resistance raising.Prepared shitosan/sulfonated polyether sulfone-polyether sulfone composite membrane is used for ethanol dehydration, has preferably dewatering.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, 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.The shitosan all rear temperature of dissolving is down 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, is down 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.Chitosan solution processed is spun on the supporting layer, and 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, corresponding separation factor is 328.
Embodiment two
Take by weighing 2.5g deacylated tRNA degree and be 90.2% shitosan, 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 is down 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, is down 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.Chitosan solution processed is spun on the supporting layer, and 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, corresponding separation factor is 376.
Embodiment three
Take by weighing 2.5g deacylated tRNA degree and be 90.2% shitosan, 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 is down 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, is down 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.Chitosan solution processed is spun on the supporting layer, and 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, corresponding separation factor is 277.
Embodiment four
Take by weighing 2.5g deacylated tRNA degree and be 90.2% shitosan, 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 is down 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, is down 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.Chitosan solution processed is spun on the supporting layer, and 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, corresponding separation factor is 124.
Embodiment five
Take by weighing 2.5g deacylated tRNA degree and be 90.2% shitosan, 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 is down 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, is down 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.Chitosan solution processed is spun on the supporting layer, and 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, corresponding separation factor is 300.
Embodiment six
Take by weighing 2.5g deacylated tRNA degree and be 90.2% shitosan, 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 is down 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, is down 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.Chitosan solution processed is spun on the supporting layer, and 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, corresponding separation factor is 291.
Comparative Examples one
Take by weighing 2.5g deacylated tRNA degree and be 90.2% shitosan, 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 is down 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, be down 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.Chitosan solution processed is spun on the supporting layer, and 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, corresponding 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; Be that 58000 polyether sulfone is dissolved in that to be mixed with mass concentration in the chloroformic solution be 6.3% homogeneous solution with mean molecule quantity, chlorosulfonic acid is dissolved in the chloroform, be mixed with mass concentration and be 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 and immerse immediately in the deionized water to get asymmetric basement membrane supporting layer, then use the spin coating instrument successively with 500r/min spin coating 10s chitosan solution processed, 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.
2. the application of the shitosan/sulfonated polyether sulfone that makes by method claimed in claim 1-polyether sulfone composite membrane, being used for ethanol/water separates, be 0.33KPa at the film downstream pressure, operating temperature is 20～80 ℃, the material liquid flow velocity is 60 l/hs, separation factor is 123～453, and permeation flux is 918～1447g/ (m
2H).
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| US20220008918A1 (en) * | 2016-07-08 | 2022-01-13 | California Institute Of Technology | Methods and devices for performing flow-through capture of low-concentration analytes |
| 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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| CN111467978B (en) * | 2020-03-03 | 2022-03-22 | 贵州省材料产业技术研究院(贵州省复合改性聚合物材料工程技术研究中心、国家复合改性聚合物材料工程技术研究中心) | Method for preparing chitosan crosslinked styrene maleic anhydride/polyether sulfone composite nanofiltration membrane |
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| CA2435538A1 (en) * | 2003-07-18 | 2005-01-18 | Universite Laval | Solvent resistant asymmetric integrally skinned membranes |
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