CN102974230B - Chitosan/titanium dioxide ultrathin hybrid film, and preparation method and application thereof - Google Patents
Chitosan/titanium dioxide ultrathin hybrid film, and preparation method and application thereof Download PDFInfo
- Publication number
- CN102974230B CN102974230B CN201210509558.3A CN201210509558A CN102974230B CN 102974230 B CN102974230 B CN 102974230B CN 201210509558 A CN201210509558 A CN 201210509558A CN 102974230 B CN102974230 B CN 102974230B
- Authority
- CN
- China
- Prior art keywords
- solution
- preparation
- chitosan
- film
- shitosan
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention relates to a chitosan/titanium dioxide ultrathin hybrid film, and a preparation method and application thereof. The preparation process comprises the following steps: preparing a chitosan acetate solution of which the mass concentration is 2wt%; sequentially adding titanium tetrachloride and 3-(3,4-dihydroxyphenyl)propionic acid into an ethanol-water mixed solution, and stirring; dropwisely adding the solution in the previous step into the prepared chitosan solution according to a certain ratio, and reacting for a certain time; adding glutaric dialdehyde, and performing crosslinking reaction; and filtering, standing, debubbling to obtain a film casting solution, performing spin coating on a polyacrylonitrile ultrafiltration film, and drying to obtain the ultrathin hybrid film. According to the invention, the conditions in the preparation process are mild, and the raw materials are abundant and controllable. The prepared ultrathin hybrid film has a thickness of 250 nm or so, can be used in processes such as dewatering of organic solvent, dehumidification of gas, desalting of solutions and the like and has excellent comprehensive properties. When the chitosan/titanium dioxide ultrathin hybrid film is used in an ethanol-water mixed system, the separation factor can be up to 730, and the permeation flux can be up to 1403g/(m<2>h).
Description
Technical field
The present invention relates to a kind of diffusion barrier and preparation method and application, especially the ultra-thin hybridized film of shitosan/titanium dioxide and preparation method and application.
Background technology
The processes such as in recent years, hydrophilic film material is widely used in dehumidification of gas, solvent dehydration, pervaporation desalination.To preferential permeable process, according to dissolving-diffusion theory, high-hydrophilic can promote the preferential absorption of water, suppresses formation and the coupling phenomenon of water cluster simultaneously, promotes the preferential diffusion of hydrone.But water, as plasticiser, can reduce active force between hydrophilic film material strand, increase chain spacing, i.e. Swelling.Excessively swelling other molecule (size is greater than hydrone) outside making to dewater in solution more easily sees through film, reduces diffusion selective.In addition, the mechanical strength of film and stability reduce, and shorten the service life of film.Therefore, how to realize and the in the situation that of high-hydrophilic, keep the problem that needs solution that further develops appropriate, that controlled anti-swelling ability is hydrophilic membrane.Conventional anti-swelling method at present, as blend, grafting, crosslinked grade is all to reduce hydrophily as cost.Due to rigid structure and the solvent resistance of inorganic component, hybrid organic-inorganic film becomes a kind of swelling method of inhibition of extensive employing.Hybridized film mainly can be prepared by two kinds of methods: physical blending and original position sol-gel.Wherein adopt IN-SITU SOL-GEL, inorganic precursor forms hydrogen bond and covalent bond with macromolecule in hydrolytie polycondensation process, thereby to the chemical crosslinking of macromolecule formation around, macromolecule-inorganic hybridization network can more effectively improve anti-swelling ability.By inorganic precursor is carried out to modification, can carry out functionalization to inorganic component, can control easily the hydrolysis condensation reaction of inorganic precursor in macromolecule simultaneously, thus generation and the hybridized film structure of regulation and control inorganic component.Metal-organic chelated is that occurring in nature is prepared hybrid material, a kind of conventional means of enhance mechanical strength, especially the function in bioadhesive albumen has obtained extensive concern at present, and its mechanism of action is widely used in the preparation of the surface modified and hybrid material of metal and oxide thereof.
Summary of the invention
The object of the present invention is to provide the ultra-thin hybridized film of a kind of shitosan/titanium dioxide and preparation method and application, is a kind of original position process for preparing sol-gel of macromolecular-inorganic hybrid membrane material.Utilize inorganic precursor and chelating agent 3-(3,4-dihydroxy phenyl) stronger chelation between propionic acid, be hydrolyzed and in polycondensation reaction forms stable hybrid cross-linked structure, limited the growth of inorganic particle at presoma, thereby give film good anti-swelling, and prepare the possibility of ultrathin membrane, the carboxyl on chelating agent has improved the hydrophily of membrane material simultaneously.Membrane material has following main feature: 1) by changing masking formula, and can be flexibly, Effective Regulation hybridized film structure and physicochemical properties; 2) inorganic component is dispersed in polymeric membrane, and between macromolecule, has multiple interaction, has higher stability; 3) preparation process is simple, and reaction condition gentleness is easily made ultrathin membrane and accomplishes scale production.Can estimate, the hybrid organic-inorganic film material that the method makes is by with its high-hydrophilic, stiff stability and appropriateness, controlled anti-swelling ability and have important researching value and prospects for commercial application.The membrane material that the method is made, for the dehydration of alcohol-water mixed system pervaporation, in the case of maintaining the permeation flux remaining basically stable with chitosan film, has good separation.
The ultra-thin hybridized film of a kind of shitosan/titanium dioxide provided by the invention is with shitosan, 3-(3,4-dihydroxy phenyl) propionic acid and titanium tetrachloride be raw material preparation, the mass ratio of shitosan and titanium tetrachloride is 100: the mol ratio of 1-28.5, titanium tetrachloride and 3-(3,4-dihydroxy phenyl) propionic acid is 4:1.
The preparation method of the ultra-thin hybridized film of a kind of shitosan/titanium dioxide provided by the invention comprises the following steps:
1) shitosan is dissolved in the acetum that mass concentration is 2wt% at 80 DEG C, and stirs and within 2 hours, be mixed with the chitosan solution that mass concentration is 2wt%.
2) titanium tetrachloride is at room temperature added by a certain percentage to (in titanium tetrachloride and solution, the volume ratio of ethanol, water is 1:10:20) in alcohol-water mixed solution, and stir 2 hours, then add 3-(3,4-dihydroxyphenyl) propionic acid, wherein the mol ratio of titanium tetrachloride and chelating agent is 4:1, and solution is stirred 1 hour.
3) solution (2) being made mixes with the chitosan solution that (1) makes, and reacts 2 hours to accelerate the polymerization of titanium tetrachloride at 60 DEG C, and in solution, titanium tetrachloride quality is chitosan mass 1% to 28.5%.
4) in the solution making to (3), add by a certain percentage glutaraldehyde, wherein the mol ratio of shitosan monomer chain link and glutaraldehyde is 60:1, at 30 DEG C, react 1 hour, after filtering and standing a few minutes deaeration, obtain casting solution, then casting solution is spun on polyacrylonitrile ultrafiltration film to the dry film forming of processing under room temperature.
Shitosan/titanium colloidal sol hybridized film that said method makes, for alcohol-water mixed system pervaporation dehydration (concentration of alcohol 90 wt%), separation is 330 to 730, permeation flux is 1403 to 1716 g/ (m
2h).
Wherein the viscosity average molecular weigh of selected shitosan can be 450,000.
The invention has the advantages that: preparation process is simple, mild condition, structure is controlled, and the hybridized film thickness making is 250nm left and right, and for the dehydration of alcohol-water mixed system pervaporation, separating property is better.
Brief description of the drawings
The permeation flux of film and the comparison diagram of separation factor in Fig. 1 embodiment and comparative example.
Fig. 2 is the section Electronic Speculum figure of comparative film made in comparative example.
Fig. 3 is the section Electronic Speculum figure of film 1 made in embodiment 1.
Fig. 4 is the section Electronic Speculum figure of film 2 made in embodiment 2.
Fig. 5 is the section Electronic Speculum figure of film 3 made in embodiment 3.
Detailed description of the invention
Embodiment 1
The shitosan that is 450,000 by viscosity average molecular weigh is dissolved in the acetum that mass concentration is 2wt% at 80 DEG C, and stirs and within 2 hours, be mixed with the chitosan solution that mass concentration is 2wt%.Titanium tetrachloride is at room temperature added to (in titanium tetrachloride and solution, the volume ratio of ethanol, water is 1:10:20) in alcohol-water mixed solution by a certain percentage, and stir 2 hours, then add by a certain percentage 3-(3,4-dihydroxyphenyl) propionic acid, wherein the mol ratio of titanium tetrachloride and chelating agent is 4:1.A certain amount of above-mentioned solution is stirred after 1 hour and mixed with chitosan solution, and in solution, titanium tetrachloride quality is chitosan mass 7.13%, reacts the polymerization with acceleration titanium tetrachloride in 2 hours at 60 DEG C.In above-mentioned solution, add by a certain percentage glutaraldehyde, wherein the mol ratio of shitosan monomer chain link and glutaraldehyde is 60:1, reacts 1 hour at 30 DEG C, after filtering and standing a few minutes deaeration, obtains casting solution.Then casting solution is spun on polyacrylonitrile ultrafiltration film, under room temperature, after dry processing, obtains film (film 1).Hybridized film is for the dehydration of alcohol-water mixed system pervaporation, and separation is 330, and permeation flux is 1494 g/ (m
2h).
Embodiment 2
The shitosan that is 450,000 by viscosity average molecular weigh is dissolved in the acetum that mass concentration is 2wt% at 80 DEG C, and stirs and within 2 hours, be mixed with the chitosan solution that mass concentration is 2wt%.Titanium tetrachloride is at room temperature added to (in titanium tetrachloride and solution, the volume ratio of ethanol, water is 1:10:20) in alcohol-water mixed solution by a certain percentage, and stir 2 hours, then add by a certain percentage 3-(3,4-dihydroxyphenyl) propionic acid, wherein the mol ratio of titanium tetrachloride and chelating agent is 4:1.A certain amount of above-mentioned solution is stirred after 1 hour and mixed with chitosan solution, and in solution, titanium tetrachloride quality is chitosan mass 14.25%, reacts the polymerization with acceleration titanium tetrachloride in 2 hours at 60 DEG C.In above-mentioned solution, add by a certain percentage glutaraldehyde, wherein the mol ratio of shitosan monomer chain link and glutaraldehyde is 60:1, reacts 1 hour at 30 DEG C, after filtering and standing a few minutes deaeration, obtains casting solution.Then casting solution is spun on polyacrylonitrile ultrafiltration film, under room temperature, after dry processing, obtains film (film 2).Hybridized film is for the dehydration of alcohol-water mixed system pervaporation, and separation is 730, and permeation flux is 1403 g/ (m
2h).
Embodiment 3
The shitosan that is 450,000 by viscosity average molecular weigh is dissolved in the acetum that mass concentration is 2wt% at 80 DEG C, and stirs and within 2 hours, be mixed with the chitosan solution that mass concentration is 2wt%.Titanium tetrachloride is at room temperature added to (in titanium tetrachloride and solution, the volume ratio of ethanol, water is 1:10:20) in alcohol-water mixed solution by a certain percentage, and stir 2 hours, then add by a certain percentage 3-(3,4-dihydroxyphenyl) propionic acid, wherein the mol ratio of titanium tetrachloride and chelating agent is 4:1.A certain amount of above-mentioned solution is stirred after 1 hour and mixed with chitosan solution, and in solution, titanium tetrachloride quality is chitosan mass 21.38%, reacts the polymerization with acceleration titanium tetrachloride in 2 hours at 60 DEG C.In above-mentioned solution, add by a certain percentage glutaraldehyde, wherein the mol ratio of shitosan monomer chain link and glutaraldehyde is 60:1, reacts 1 hour at 30 DEG C, after filtering and standing a few minutes deaeration, obtains casting solution.Then casting solution is spun on polyacrylonitrile ultrafiltration film, under room temperature, after dry processing, obtains film (film 3).Hybridized film is for the dehydration of alcohol-water mixed system pervaporation, and separation is 403, and permeation flux is 1463 g/ (m
2h).
Comparative example 1
The shitosan that is 450,000 by viscosity average molecular weigh is dissolved in the acetum that mass concentration is 2wt% at 80 DEG C, and stirs and within 2 hours, be mixed with the chitosan solution that mass concentration is 2wt%.In above-mentioned solution, add by a certain percentage glutaraldehyde, wherein the mol ratio of shitosan monomer chain link and glutaraldehyde is 60:1, reacts 1 hour at 30 DEG C, after filtering and standing a few minutes deaeration, obtains casting solution.Then casting solution is spun on polyacrylonitrile ultrafiltration film, under room temperature, after dry processing, obtains film (comparative film).Hybridized film is for the dehydration of alcohol-water mixed system pervaporation, and separation is 241, and permeation flux is 1496 g/ (m
2h).
Claims (9)
1. the ultra-thin hybridized film of shitosan/titanium dioxide, it is characterized in that it is with shitosan, 3-(3,4-dihydroxy phenyl) propionic acid and titanium tetrachloride be raw material preparation, the mass ratio of shitosan and titanium tetrachloride is 100: the mol ratio of 1-28.5, titanium tetrachloride and 3-(3,4-dihydroxy phenyl) propionic acid is 4:1.
2. a preparation method for the ultra-thin hybridized film of shitosan/titanium dioxide as claimed in claim 1, is characterized in that it comprises the following steps:
1) at 80 DEG C, shitosan is dissolved in acetum, and stirs and within 2 hours, be mixed with chitosan solution;
2) under room temperature, titanium tetrachloride is added in alcohol-water mixed solution, stir 2 hours, add 3-(3,4-dihydroxy phenyl) propionic acid, solution
Transparent redness, stirs 1 hour;
3) step 2) chitosan solution that makes with step 1) of the solution that makes mixes, reacts 2 hours at 60 DEG C;
4) in the solution that step 3) makes, add glutaraldehyde, react 1 hour at 30 DEG C, after filtering and standing a few minutes deaeration, obtain casting solution;
5) casting solution is spun on polyacrylonitrile ultrafiltration film to the dry film forming of processing under room temperature.
3. preparation method according to claim 2, is characterized in that the acetum mass concentration described in step 1) is 2wt%.
4. preparation method according to claim 2, is characterized in that the chitosan mass concentration described in step 1) is 2wt%.
5. preparation method according to claim 2, is characterized in that step 2) volume ratio of ethanol, water is in described titanium tetrachloride and solution
1:10:?20。
6. preparation method according to claim 2, is characterized in that step 2) described 3-(3,4-dihydroxy phenyl) propionic acid and titanium tetrachloride
Mol ratio is 1: 4.
7. preparation method according to claim 2, is characterized in that 1 wt% that in the solution described in step 3), titanium tetrachloride quality is chitosan mass
To 28.5 wt%.
8. preparation method according to claim 2, is characterized in that shitosan monomer chain link described in step 4) and the mol ratio of glutaraldehyde are 60:1.
9. the application of the ultra-thin hybridized film of shitosan/titanium dioxide as claimed in claim 1 in the dehydration of alcohol-water mixed system pervaporation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210509558.3A CN102974230B (en) | 2012-12-04 | 2012-12-04 | Chitosan/titanium dioxide ultrathin hybrid film, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210509558.3A CN102974230B (en) | 2012-12-04 | 2012-12-04 | Chitosan/titanium dioxide ultrathin hybrid film, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102974230A CN102974230A (en) | 2013-03-20 |
| CN102974230B true CN102974230B (en) | 2014-10-29 |
Family
ID=47848748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210509558.3A Expired - Fee Related CN102974230B (en) | 2012-12-04 | 2012-12-04 | Chitosan/titanium dioxide ultrathin hybrid film, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102974230B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103962013A (en) * | 2014-04-17 | 2014-08-06 | 天津大学 | Chitosan-ferroferric oxide hybrid membrane as well as preparation method and application thereof |
| CN105385248B (en) * | 2015-10-30 | 2017-05-24 | 三棵树涂料股份有限公司 | Preparation method of chitosan-supported titanium dioxide finish coating |
| CN106179242B (en) * | 2016-07-25 | 2019-09-27 | 华东理工大学 | A kind of preparation method and applications of biscuit cross-linked chitosan adsorbent |
| WO2019090470A1 (en) * | 2017-11-07 | 2019-05-16 | 蔡燕铃 | Highly permeable and highly selective pva/ga/cs-m+ pervaporation film for dehydration of organic solutions |
| CN108499373A (en) * | 2018-04-09 | 2018-09-07 | 吕莉 | A kind of preparation method of super hydrophilic oleophobic type film base water-oil separating material |
| CN111330362A (en) * | 2020-03-11 | 2020-06-26 | 天津大学 | Natural polymer-based functional air filtering material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1827225A (en) * | 2006-04-07 | 2006-09-06 | 南京工业大学 | Method for preparing TiO2 photocatalytic film doped with non-metallic element |
| CN101624449A (en) * | 2009-07-23 | 2010-01-13 | 天津大学 | Organic phosphorylated titanium dioxide micrballon-filled chitosan hybrid membrane as well as preparation and application |
| CN102008902A (en) * | 2010-10-13 | 2011-04-13 | 天津大学 | Bacterial cellulose-inorganic nanoparticle hybrid membrane and preparation method thereof |
| CN102108132A (en) * | 2011-01-19 | 2011-06-29 | 天津大学 | Preparation method and application of sulfonated polyether-ether-ketone-carboxylated titanium dioxide hybrid membrane |
-
2012
- 2012-12-04 CN CN201210509558.3A patent/CN102974230B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1827225A (en) * | 2006-04-07 | 2006-09-06 | 南京工业大学 | Method for preparing TiO2 photocatalytic film doped with non-metallic element |
| CN101624449A (en) * | 2009-07-23 | 2010-01-13 | 天津大学 | Organic phosphorylated titanium dioxide micrballon-filled chitosan hybrid membrane as well as preparation and application |
| CN102008902A (en) * | 2010-10-13 | 2011-04-13 | 天津大学 | Bacterial cellulose-inorganic nanoparticle hybrid membrane and preparation method thereof |
| CN102108132A (en) * | 2011-01-19 | 2011-06-29 | 天津大学 | Preparation method and application of sulfonated polyether-ether-ketone-carboxylated titanium dioxide hybrid membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102974230A (en) | 2013-03-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102974230B (en) | Chitosan/titanium dioxide ultrathin hybrid film, and preparation method and application thereof | |
| CN107983173B (en) | High-flux covalent organic framework composite membrane and preparation method thereof | |
| Jana et al. | Chitosan based ceramic ultrafiltration membrane: Preparation, characterization and application to remove Hg (II) and As (III) using polymer enhanced ultrafiltration | |
| CN104801208B (en) | Sodium alginate-flaky ZIF-8 hybrid composite membrane, and preparation and application thereof | |
| CN110026097B (en) | Preparation method of PIM-1@ MOFs/polymer composite pervaporation membrane | |
| Chen et al. | Engineering nanocomposite metal-phenolic network membranes with hollow MOFs via in-situ etching for High-efficiency organic solvent nanofiltration | |
| CN101905122B (en) | Self-assembly method for high-load inorganic nano particle hybridized organic membrane | |
| Lin et al. | Preparation of porous PMMA/Na+–montmorillonite cation-exchange membranes for cationic dye adsorption | |
| CN102824856B (en) | Preparation method for generating inorganic nanoparticle hybrid membrane in situ by using self-assembly technology | |
| CN103599705B (en) | The method of organic/inorganic hybrid membrane is prepared in a kind of ultrasonic immersing | |
| CN1427864A (en) | Polymer membranes | |
| CN108465377A (en) | A kind of preparation method of regenerated cellulose/chitosan composite antibiotic NF membrane | |
| Habibi et al. | Enhanced water flux through ultrafiltration polysulfone membrane via addition‐removal of silica nano‐particles: Synthesis and characterization | |
| CN103331108B (en) | Polymer pervaporation membrane prepared by dialysis method after membrane formation and preparation method of polymer pervaporation membrane | |
| Saranya et al. | Functionalised activated carbon modified polyphenylsulfone composite membranes for adsorption enhanced phenol filtration | |
| KR101171983B1 (en) | Organic-inorganic composite compositions, preparation methods thereof, water treatment membranes and water treatment modules comprising the same | |
| JP6088932B2 (en) | Separation membrane comprising inorganic / organic hybrid compound and method for producing the same | |
| CN101402023A (en) | Antimicrobial flat-plate separation film and method of producing the same | |
| CN102489180A (en) | Preparation method for composite porous filter membrane made of high polymer/nano material | |
| CN113813801B (en) | Mixed matrix ultrafiltration membrane doped with ZIFs@polyionic liquid compound and preparation method thereof | |
| CN110799260B (en) | Crosslinked polymer film and method for producing same | |
| CN101768351A (en) | Method for preparing mesoporous nano particle-enhanced nylon composite material | |
| CN112933981B (en) | Ethanol selective pervaporation composite membrane, preparation method thereof and method for separating and purifying ethanol | |
| Yang et al. | Fabricating a ZIF‐8@ Polydimethylsiloxane (PDMS)/PVDF mixed matrix composite membrane for separation of ethanol from aqueous solution via vapor permeation | |
| CN113318603A (en) | Organic-inorganic hybrid separation membrane and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141029 Termination date: 20201204 |