CN105879723A - Chitosan/nonionic surfactant cross-linked gel film with sandwich structure and preparation method thereof - Google Patents

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

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CN105879723A
CN105879723A CN201410783999.1A CN201410783999A CN105879723A CN 105879723 A CN105879723 A CN 105879723A CN 201410783999 A CN201410783999 A CN 201410783999A CN 105879723 A CN105879723 A CN 105879723A
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cross
gel film
nonionic surfactant
sandwich structure
chitosan
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CN105879723B (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/nonionic surfactant 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, nonionic surfactant 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 0.1-6 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/nonionic surfactant 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/nonionic surfactant cross-linked gel film with the sandwich structure is formed, the nonionic surfactant 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/nonionic surfactant 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/nonionic surfactant crosslinking solidifying Glued membrane and preparation method thereof.
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. A kind of nonionic surfactant gel gas separation membrane disclosed in Chinese patent CN102489182A and preparation method thereof, institute Selecting functional vector is polysorbas20, Tween 80 etc., has obtained the gel film that gas permselective property can be good.Chinese patent CN103599707A and CN103657441A discloses the preparation method of several support ionic liquid gel film, also obtains Relatively high permeating flux and the gel film of separation selectivity.But it is poor generally to there is mechanical property in existing gel film, structural instability, The problems such as functional vector easily spilling, are 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/ Nonionic surfactant 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 Base and isocyanate groups carry out active hydrogen reaction, it is achieved the surface cross linking of gel film, form sandwich structure.Keeping it high Permeation flux and high score, on the basis of selective, be obviously improved the mechanical property of film, prepared and have high permeating flux, height The cross-linked gel film of separation selectivity and excellent mechanical performances and stability, great commercial Application potentiality.
A kind of sandwich structure chitosan/nonionic surfactant cross-linked gel film that the present invention proposes and preparation method thereof, it is special Levy and be to comprise the steps:
A is flat after chitosan 10-20 part, solvent 70-80 part and nonionic surfactant 10-20 part uniformly being mixed at 30-50 DEG C It is layered on polyfluortetraethylene plate, dry out solvent, prepares gel film；
1-3 part cross-linking agent and 1-2 are dripped catalyst and are dissolved in 97-99 part normal hexane formation cross-linking agent solution by B, by above-mentioned gel film submergence In this cross-linking agent solution 0.1～6 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/nonionic surfactant cross-linked gel film.
Preferably, described nonionic surfactant is polysorbas20, tween 21, polysorbate60, polysorbate65, Tween 80, QULA Logical X-100, TritonX X-114, span 20, sorbester p18, sorbester p17 or sorbester p37.
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/nonionic surfactant cross-linked gel film that the present invention provides has three-decker, upper layer For cross-linked layer, thickness is between 2-8 micron；Centre is gel layer, and thickness is between 50-75 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 is nonionic surfactant, has the strongest solvability to carbon dioxide, simultaneously safety non-toxic, cheap, is The gelatinous mass being applicable to gas separation of very attractive.Sandwich structure chitosan/non-ionic surface active that the present invention prepares Agent cross-linked gel film has high permeation flux and separation selectivity, simultaneously satisfactory mechanical property, and stability is excellent.
In sum, sandwich structure chitosan of the present invention/nonionic surfactant cross-linked gel film and preparation method thereof Have the advantage that
1, the chitosan aboundresources that the present invention selects, low price, safety and environmental protection, chemically reactive modification, biodegradable.
2, the nonionic surfactant that the present invention uses has extremely strong dissolving selectivity to carbon dioxide, the most nontoxic non-stimulated, Structure is more stable.
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 liquid non-ionic surfactant, it is provided that high permeating flux and separation Selectivity.
Detailed description of the invention:
The following is the embodiment of sandwich structure chitosan/nonionic surfactant cross-linked gel film and preparation method thereof, but described Embodiment is not construed as limiting the invention.
Embodiment one:
(1) gel film is prepared:
By aqueous acetic acid that 10 parts of chitosans, 75 parts of mass fractions are 2% and 15 parts of polysorbas20s at 40 DEG C after mix homogeneously It is laid on polyfluortetraethylene plate, dry out solvent, prepares gel film.
(2) film top layer cross-links again:
2 parts of isophorone diisocyanate 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 0.1 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/nonionic surfactant cross-linked gel film.
Above-mentioned sandwich structure chitosan/nonionic surfactant cross-linked gel film is used for CO2/N2Separate, at 30 DEG C and Under the test condition of 0.06MPa, CO2Infiltration coefficient be 197barrer, CO2/N2Ideal selectivity be 63.81.
Embodiment two:
(1) gel film is prepared:
Aqueous acetic acid and 10 parts of TritonX X-114 that 20 parts of chitosans, 70 parts of mass fractions are 3% are mixed at 30 DEG C It is laid in after Jun Yun on polyfluortetraethylene plate, dry out solvent, prepares gel film.
(2) film top layer cross-links again:
1 part of toluene di-isocyanate(TDI) and 1 dibutyl tin laurate are dissolved in 99 parts of normal hexane formation cross-linking agent solution, will Above-mentioned gel film is immersed in this cross-linking agent solution 6 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/nonionic surfactant cross-linked gel film.
Above-mentioned sandwich structure chitosan/nonionic surfactant cross-linked gel film is used for CO2/N2Separate, at 30 DEG C and Under the test condition of 0.06MPa, CO2Infiltration coefficient be 107barrer, CO2/N2Ideal selectivity be 123.84.
Embodiment three:
(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 sorbester p17s at 50 DEG C after mix homogeneously It is laid on polyfluortetraethylene plate, dry out solvent, prepares gel film.
(2) film top layer cross-links again:
3 parts of methyl diphenylene diisocyanates and 2 dibutyl tin laurates are dissolved in 97 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/nonionic surfactant cross-linked gel film.
Above-mentioned sandwich structure chitosan/nonionic surfactant cross-linked gel film is used for CO2/N2Separate, at 30 DEG C and Under the test condition of 0.06MPa, CO2Infiltration coefficient be 221barrer, CO2/N2Ideal selectivity be 74.84.
Embodiment four:
(1) gel film is prepared:
By aqueous acetic acid that 10 parts of chitosans, 80 parts of mass fractions are 2% and 10 parts of Tween 80s at 40 DEG C after mix homogeneously It is laid on polyfluortetraethylene plate, dry out solvent, prepares gel film.
(2) film top layer cross-links again:
3 parts of hexamethylene diisocyanates and 2 dibutyl tin laurates are dissolved in 97 parts of normal hexane formation cross-linking agent molten Liquid, is immersed in above-mentioned gel film 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/nonionic surfactant cross-linked gel film.
Above-mentioned sandwich structure chitosan/nonionic surfactant cross-linked gel film is used for CO2/N2Separate, at 30 DEG C and Under the test condition of 0.06MPa, CO2Infiltration coefficient be 143barrer, CO2/N2Ideal selectivity be 110.43.
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/nonionic surfactant cross-linked gel film, it is characterised in that include as follows Step:
A is flat after chitosan 10-20 part, solvent 70-80 part and nonionic surfactant 10-20 part uniformly being mixed at 30-50 DEG C It is layered on polyfluortetraethylene plate, dry out solvent, prepares gel film；
1-3 part cross-linking agent and 1-2 are dripped catalyst and are dissolved in 97-99 part normal hexane formation cross-linking agent solution by B, are soaked by above-mentioned gel film Not in this cross-linking agent solution 0.1～6 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/nonionic surfactant cross-linked gel film.
The most according to claim 1, the preparation method of sandwich structure chitosan/nonionic surfactant cross-linked gel film, it is special Levying and be, described nonionic surfactant is polysorbas20, tween 21, polysorbate60, polysorbate65, Tween 80, TritonX X-100, TritonX X-114, span 20, sorbester p18, sorbester p17 or sorbester p37.
3., according to the preparation method of sandwich structure chitosan described in claim 1-2/nonionic surfactant cross-linked gel film, it is special Levying and be, described cross-linking agent is methyl diphenylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate Or toluene di-isocyanate(TDI).
4., according to the preparation method of sandwich structure chitosan described in claim 1-3/nonionic surfactant cross-linked gel film, it is special Levying and be, described catalyst is dibutyl tin laurate.
5., according to the preparation method of sandwich structure chitosan described in claim 1-4/nonionic surfactant cross-linked gel film, it is special Levy and be, described solvent be mass fraction be the aqueous acetic acid of 1-3%.
6. sandwich structure chitosan/nonionic surfactant cross-linked gel film, it is characterised in that described gel film has three Rotating fields, upper layer is cross-linked layer, and thickness is between 2-8 micron；Centre is gel layer, and thickness is between 50-75 micron.
CN201410783999.1A 2014-12-16 2014-12-16 A kind of sandwich structure chitosan/nonionic surfactant cross-linked gel film and preparation method thereof Active CN105879723B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113444472A (en) * 2021-08-31 2021-09-28 江苏万淇生物科技股份有限公司 Preparation method of surfactant composite adhesive film

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102489182A (en) * 2011-12-15 2012-06-13 江南大学 Nonionic surfactant gel and gas separating membrane and preparation method thereof
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
WO2014157069A1 (en) * 2013-03-29 2014-10-02 株式会社ルネッサンス・エナジー・リサーチ Facilitated co2 transport membrane, method for manufacturing same, resin composition to be used in method for manufacturing same, co2 separation module, co2 separation method and co2 separation device
CN104174305A (en) * 2013-09-02 2014-12-03 天津森诺过滤技术有限公司 Biodegradable separation membrane

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102489182A (en) * 2011-12-15 2012-06-13 江南大学 Nonionic surfactant gel and gas separating membrane and preparation method thereof
WO2014157069A1 (en) * 2013-03-29 2014-10-02 株式会社ルネッサンス・エナジー・リサーチ Facilitated co2 transport membrane, method for manufacturing same, resin composition to be used in method for manufacturing same, co2 separation module, co2 separation method and co2 separation device
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
CN104174305A (en) * 2013-09-02 2014-12-03 天津森诺过滤技术有限公司 Biodegradable separation membrane

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113444472A (en) * 2021-08-31 2021-09-28 江苏万淇生物科技股份有限公司 Preparation method of surfactant composite adhesive film
CN113444472B (en) * 2021-08-31 2021-10-29 江苏万淇生物科技股份有限公司 Preparation method of surfactant composite adhesive film

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