CN105879722A - Chitosan/ionic liquid cross-linked gel film with sandwich structure and preparation method thereof - Google Patents

Chitosan/ionic liquid cross-linked gel film with sandwich structure and preparation method thereof Download PDF

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CN105879722A
CN105879722A CN201410783998.7A CN201410783998A CN105879722A CN 105879722 A CN105879722 A CN 105879722A CN 201410783998 A CN201410783998 A CN 201410783998A CN 105879722 A CN105879722 A CN 105879722A
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gel film
cross
ionic liquid
sandwich structure
chitosan
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CN105879722B (en
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张春芳
张鹏
白云翔
顾瑾
孙余凭
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Jiangnan University
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Jiangnan University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

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Abstract

The invention belongs to the technical field of film separation and relates to a chitosan/ionic liquid cross-linked gel film with a sandwich structure and a preparation method thereof. The film is characterized in that the film has the sandwich structure, the upper and lower surface layers are arranged as cross-linked surfaces and a gel layer is arranged in the middle. The preparation method comprises the following steps: (1) uniformly mixing chitosan, ionic liquid and solvent under a certain temperature, paving on a polytetrafluoroethylene plate, and drying to remove the solvent to obtain a gel film; (2) soaking the gel film in the solution containing the cross-linking agent and catalyst for 0.2-12 hours and performing the surface cross-linking reaction on the gel film; (3) drying the cross-linked gel film in air for 24 hours, and then transferring into a vacuum drying oven, and processing for 24 hours at 30 DEG C, thereby acquiring the chitosan/ionic liquid cross-linked gel film with the sandwich structure. According to the preparation method provided by the invention, the upper and lower surfaces of the film are cross-linked, so that the chitosan/ionic liquid cross-linked gel film with the sandwich structure is formed, the ionic liquid is difficult to run off, the lasting stability of the physical structure and property of the film is ensured and the preparation method is fit for the separating of the carbon dioxide in the mixed gas and the recycling of the organic steam.

Description

A kind of sandwich structure chitosan/ionic liquid cross-linked gel film and preparation method thereof
Technical field
The invention belongs to technical field of membrane separation, particularly relate to a kind of sandwich structure chitosan/ionic liquid cross-linked gel film and Preparation method.
Background technology
CO in current atmospheric2Concentration constantly rises, and greenhouse effect increasingly sharpens, and the ecological environment depending on the mankind for existence causes Serious threat.Conventional CO2Isolation technics, such as amine aqueous solution absorption process, separation by deep refrigeration and pressure swing adsorption method, is realizing Along with high energy consumption, high operating cost or the possibility that there is secondary pollution during gas separation.Therefore, there is economy, height The membrane separation technique of the plurality of advantages such as effect, environmental protection receives more and more attention at gas separation field.
Gel film is the novel film materials of rising in recent years, high molecular polymer and functional vector collectively constitute.Polymer divides Son forms spacial framework by effects such as crystallization, crosslinking or hydrogen bonds, holds onto liquid function carrier so that it is be uniformly dispersed In the hole of network structure thus form stable self-supporting system.As a kind of between solid-state and and the particular matter of liquid, Gel film has the high stability of polymeric film, and the high pass of liquid film concurrently, is separating CO2Aspect has a good application prospect. Chinese patent CN103599707A and CN103657441A discloses the preparation method of several support ionic liquid gel film, Selected function carrier is 1-octyl group-3-vinyl imidazole hexafluorophosphate and 1-ethyl-3-methylimidazole bis-trifluoromethylsulfoandimide Salt etc., have obtained the gel film that gas permselective property can be good.Chinese patent CN102489182A and CN103599712A In disclose several tenside gel film and preparation method thereof, also obtain the gel of relatively high permeating flux and separation selectivity Gas separation membrane.But it is poor that existing gel film generally exists mechanical property, structural instability, functional vector easily spilling etc. is asked Topic, is unfavorable for the industrial applications of reality.
Summary of the invention
It is an object of the invention to the deficiency overcoming existing gel film at gas separation field, it is provided that a kind of sandwich structure chitosan/ Ionic liquid cross-linked gel film and preparation method thereof.The present invention is by by the amino in the chitosan of gel film top layer and hydroxyl and isocyanide Acid esters group reacts, it is achieved the surface cross linking of gel film, forms sandwich structure.Keeping its high permeating flux and high score On the basis of selective, be obviously improved the mechanical property of film, prepare have high permeating flux, high separation selectivity and The cross-linked gel film of excellent mechanical performances and stability, great commercial Application potentiality.
A kind of sandwich structure chitosan/ionic liquid cross-linked gel film that the present invention proposes and preparation method thereof, it is characterised in that bag Include following steps:
A is laid in poly-four after chitosan 10-20 part, solvent 70-80 part and ionic liquid 10-20 part uniformly being mixed at 30-50 DEG C On fluorothene plate, dry out solvent, prepare gel film；
1-5 part cross-linking agent and 1-2 are dripped catalyst and are dissolved in 95-99 part normal hexane formation cross-linking agent solution by B, are soaked by above-mentioned gel film Not in this cross-linking agent solution 0.2～12 hour, carry out gel film surface cross linking；
Gel film after crosslinking is dried 24 hours by C in atmosphere, then proceeds in vacuum drying oven, processes 24 hours at 30 DEG C, Obtain sandwich structure chitosan/ionic liquid cross-linked gel film.
Preferably, the cation of described ionic liquid is imidazoles, and anion is borofluoride, fluorophosphate or double fluoroform sulphonyl Inferior amine salt.
Preferably, described cross-linking agent is methyl diphenylene diisocyanate, isophorone diisocyanate, hexa-methylene two isocyanide Acid esters or toluene di-isocyanate(TDI).
Preferably, described catalyst is dibutyl tin laurate.
Preferably, described solvent be mass fraction be the aqueous acetic acid of 1-3%.
Sandwich structure chitosan/ionic liquid cross-linked gel film that the present invention provides has three-decker, and upper layer is crosslinking Layer, thickness is between 5-10 micron；Centre is gel layer, and thickness is between 60-80 micron.
Polymeric matrix selected by the present invention is chitosan, and this material is a kind of natural polymer biomass resource, has raw material rich Richness, safety non-toxic, environmental protection and the plurality of advantages such as biodegradable, be dispersed with numerous character relatively on chitosan molecule chain simultaneously Active amino and hydroxyl, lay a good foundation for its chemical modification, is a kind of preferably macromolecule polymer material.Selected function Property carrier be ionic liquid, it has a special affinity to carbon dioxide, the most volatile, structure-controllable, be a kind of for The ideal gel material that gas separates.The sandwich structure chitosan that the present invention prepares/ionic liquid cross-linked gel film has high oozing Flux and separation selectivity, satisfactory mechanical property simultaneously thoroughly, stability is excellent.
In sum, sandwich structure chitosan of the present invention/ionic liquid cross-linked gel film and preparation method thereof has following Advantage:
1, the chitosan aboundresources that the present invention selects, low price, safety and environmental protection, chemically reactive modification, biodegradable.
2, the ionic liquid that the present invention uses has special affinity to carbon dioxide, the most volatile, structure-controllable.
3, the cross-linking process of inventive gel film relates to interfacial reaction, and top layer is cross-linked layer, and even compact improves good mechanics Performance and stability；Centre is gel layer, is full of ionic liquid, it is provided that high permeating flux and separation selectivity.
Detailed description of the invention:
The following is the embodiment of sandwich structure chitosan/ionic liquid cross-linked gel film and preparation method thereof, but described embodiment is not It is construed as limiting the invention.
Embodiment one:
(1) gel film is prepared:
By aqueous acetic acid that 10 parts of chitosans, 70 parts of mass fractions are 2% and 20 parts of 1-methyl-3-ethyl imidazol(e) hexafluorophosphoric acids Salt is laid on polyfluortetraethylene plate after mix homogeneously at 50 DEG C, dry out solvent, prepares gel film.
(2) film top layer cross-links again:
2 parts of methyl diphenylene diisocyanates and 2 dibutyl tin laurates are dissolved in 98 parts of normal hexane formation cross-linking agent molten Liquid, is immersed in above-mentioned gel film in this cross-linking agent solution 0.5 hour, carries out gel film surface cross linking；
(3) post processing:
Gel film after crosslinking is dried 24 hours in atmosphere, then proceeds in vacuum drying oven, process 24 hours at 30 DEG C, Obtain sandwich structure chitosan/ionic liquid cross-linked gel film.
Above-mentioned sandwich structure chitosan/ionic liquid cross-linked gel film is used for CO2/N2Separate, at 30 DEG C and 0.06MPa Under test condition, CO2Infiltration coefficient be 313barrer, CO2/N2Ideal selectivity be 72.65.
Embodiment two:
(1) gel film is prepared:
By aqueous acetic acid that 10 parts of chitosans, 80 parts of mass fractions are 3% and 10 parts of 1-octyl group-3-Methylimidazole. Tetrafluoroboric acids Salt is laid on polyfluortetraethylene plate after mix homogeneously at 40 DEG C, dry out solvent, prepares gel film.
(2) film top layer cross-links again:
5 parts of isophorone diisocyanate and 1 dibutyl tin laurate are dissolved in 95 parts of normal hexane formation cross-linking agent molten Liquid, is immersed in above-mentioned gel film in this cross-linking agent solution 0.2 hour, carries out gel film surface cross linking；
(3) post processing:
Gel film after crosslinking is dried 24 hours in atmosphere, then proceeds in vacuum drying oven, process 24 hours at 30 DEG C, Obtain sandwich structure chitosan/ionic liquid cross-linked gel film.
Above-mentioned sandwich structure chitosan/ionic liquid cross-linked gel film is used for CO2/N2Separate, at 30 DEG C and 0.06MPa Under test condition, CO2Infiltration coefficient be 276barrer, CO2/N2Ideal selectivity be 86.95.
Embodiment three:
(1) gel film is prepared:
By aqueous acetic acid that 20 parts of chitosans, 80 parts of mass fractions are 3% and 10 parts of double fluoroforms of 1-butyl-3-Methylimidazole. Sulfimide salt is laid on polyfluortetraethylene plate after mix homogeneously at 40 DEG C, dry out solvent, prepares gel film.
(2) film top layer cross-links again:
2 parts of hexamethylene diisocyanates and 2 dibutyl tin laurates are dissolved in 98 parts of normal hexane formation cross-linking agent molten Liquid, is immersed in above-mentioned gel film in this cross-linking agent solution 12 hours, carries out gel film surface cross linking；
(3) post processing:
Gel film after crosslinking is dried 24 hours in atmosphere, then proceeds in vacuum drying oven, process 24 hours at 30 DEG C, Obtain sandwich structure chitosan/ionic liquid cross-linked gel film.
Above-mentioned sandwich structure chitosan/ionic liquid cross-linked gel film is used for CO2/N2Separate, at 30 DEG C and 0.06MPa Under test condition, CO2Infiltration coefficient be 143barrer, CO2/N2Ideal selectivity be 139.65.
Embodiment four:
(1) gel film is prepared:
By aqueous acetic acid that 10 parts of chitosans, 75 parts of mass fractions are 3% and 15 parts of 1-butyl-3-ethyl imidazol(e) hexafluorophosphoric acids Salt is laid on polyfluortetraethylene plate after mix homogeneously at 30 DEG C, dry out solvent, prepares gel film.
(2) film top layer cross-links again:
4 parts of toluene di-isocyanate(TDI)s and 2 dibutyl tin laurates are dissolved in 96 parts of normal hexane formation cross-linking agent solution, will Above-mentioned gel film is immersed in this cross-linking agent solution 3 hours, carries out gel film surface cross linking；
(3) post processing:
Gel film after crosslinking is dried 24 hours in atmosphere, then proceeds in vacuum drying oven, process 24 hours at 30 DEG C, Obtain sandwich structure chitosan/ionic liquid cross-linked gel film.
Above-mentioned sandwich structure chitosan/ionic liquid cross-linked gel film is used for CO2/N2Separate, at 30 DEG C and 0.06MPa Under test condition, CO2Infiltration coefficient be 176barrer, CO2/N2Ideal selectivity be 99.87.
The description of above-described embodiment should be considered explanation, it is easy to is understood by, can be without departing from illustrating the most in detail in the claims The present invention in the case of use many changes and the combination of feature described above, this kind of change has been not to be regarded as a departure from this Bright spirit and scope, and all such change be included in the range of claims below.

Claims (6)

1. the preparation method of sandwich structure chitosan/ionic liquid cross-linked gel film, it is characterised in that comprise the steps:
A is laid in poly-four after chitosan 10-20 part, solvent 70-80 part and ionic liquid 10-20 part uniformly being mixed at 30-50 DEG C On fluorothene plate, dry out solvent, prepare gel film；
1-5 part cross-linking agent and 1-2 are dripped catalyst and are dissolved in 95-99 part normal hexane formation cross-linking agent solution by B, are soaked by above-mentioned gel film Not in this cross-linking agent solution 0.2～12 hour, carry out gel film surface cross linking；
Gel film after crosslinking is dried 24 hours by C in atmosphere, then proceeds in vacuum drying oven, processes 24 hours at 30 DEG C, Obtain sandwich structure chitosan/ionic liquid cross-linked gel film.
The preparation method of sandwich structure chitosan/ionic liquid cross-linked gel film the most according to claim 1, it is characterised in that The cation of described ionic liquid is imidazoles, and anion is borofluoride, fluorophosphate or bis-trifluoromethylsulfoandimide salt.
3. according to the preparation method of sandwich structure chitosan described in claim 1-2/ionic liquid cross-linked gel film, it is characterised in that Described cross-linking agent is methyl diphenylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or toluene two Isocyanates.
4. according to the preparation method of sandwich structure chitosan described in claim 1-3/ionic liquid cross-linked gel film, it is characterised in that Described catalyst is dibutyl tin laurate.
5. according to the preparation method of sandwich structure chitosan described in claim 1-4/ionic liquid cross-linked gel film, it is characterised in that Described solvent be mass fraction be the aqueous acetic acid of 1-3%.
6. sandwich structure chitosan/ionic liquid cross-linked gel film, it is characterised in that described gel film has three-decker, Upper layer is cross-linked layer, and thickness is between 5-10 micron；Centre is gel layer, and thickness is between 60-80 micron.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111359453A (en) * 2020-03-21 2020-07-03 山东科技大学 Imidazole-doped ionic liquid/modified chitosan homogeneous anion exchange membrane and preparation method thereof
CN113398775A (en) * 2020-03-17 2021-09-17 四川大学 Functional ionic liquid-gelatin composite membrane and preparation method thereof

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CN103203187A (en) * 2012-01-14 2013-07-17 北京化工大学 A preparation method for solid film dip-coated with a novel chiral recognition agent
CN103242554A (en) * 2013-05-13 2013-08-14 中国科学院化学研究所 Nanometer plural gel and preparation method thereof
CN103372377A (en) * 2012-04-25 2013-10-30 同济大学 Preparation method of imidazole-type ion liquid gel supported liquid membrane for gas separation

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CN103203187A (en) * 2012-01-14 2013-07-17 北京化工大学 A preparation method for solid film dip-coated with a novel chiral recognition agent
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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN113398775A (en) * 2020-03-17 2021-09-17 四川大学 Functional ionic liquid-gelatin composite membrane and preparation method thereof
CN113398775B (en) * 2020-03-17 2022-06-28 四川大学 Functional ionic liquid-gelatin composite membrane and preparation method thereof
CN111359453A (en) * 2020-03-21 2020-07-03 山东科技大学 Imidazole-doped ionic liquid/modified chitosan homogeneous anion exchange membrane and preparation method thereof

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