CN101671445B - Method for preparing chitosan/silicon dioxide hybridization barrier packaging composite film - Google Patents
Method for preparing chitosan/silicon dioxide hybridization barrier packaging composite film Download PDFInfo
- Publication number
- CN101671445B CN101671445B CN200910153634XA CN200910153634A CN101671445B CN 101671445 B CN101671445 B CN 101671445B CN 200910153634X A CN200910153634X A CN 200910153634XA CN 200910153634 A CN200910153634 A CN 200910153634A CN 101671445 B CN101671445 B CN 101671445B
- Authority
- CN
- China
- Prior art keywords
- chitosan
- silicon dioxide
- film
- packaging
- preparation
- 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
Abstract
The invention discloses a method for preparing a chitosan/silicon dioxide hybridization barrier packaging composite film, comprising the following steps: carrying out acid oxidation treatment to the packaging film; preparing silicon dioxide sol by adopting tetraethoxysilane, silane coupling agent, alcohol and deionized water; mixing chitosan solution and silicon dioxide sol and preparing chitosan/silicon dioxide hybridization sol; adopting a dipping-pulling method to coat the chitosan /silicon dioxide hybridization sol on the packaging film after the acid oxidation treatment, and drying. In the invention, the natural polymer chitosan is adopted as organic phase, a chitosan/silicon dioxide organic-inorganic hybridization barrier layer is loaded on a packaging film substrate with poorer thermal resistance, and the hybridization barrier layer and the packaging film are closely attached to jointly form the chitosan/silicon dioxide organic-inorganic hybridization barrier packaging composite film. The invention has simple preparation process and low cost; and the prepared chitosan/silicon dioxide hybrid packaging composite film has remarkably improved barrier property as well as excellent mechanical property and optical property.
Description
Technical field
The present invention relates to prepare the method for chitosan/silicon dioxide hybridization barrier packaging composite film, belong to the packaging film technical field.
Background technology
Polyolefins, polyester, packaging film commonly used such as polyamide-based are owing to transparent, easy processing, advantage such as cheap are widely used in packaging field, but gases such as oxygen, carbonic acid gas, water vapour see through easily and influence the performance and the life-span of packed article.In order to improve the barrier property of packaging film, usually adopt technology such as chemical vapour deposition, physical vapor deposition at present at barrier layers such as packaging film surface deposition silicon oxide, titanium oxide, aluminum oxide, silicon nitrides, barrier packaging film with high comprehensive performances such as preparation optical property, mechanical properties, but complex process, the cost height.
Sol-gel method craft is simple, is easy to moulding and doping, can carry out molecular designing and cut out by the composition of control reactant, and be one of important method of preparation function film.But present research about sol-gel method mainly concentrates on and prepare function films such as photocatalysis thin film, hydrophilic film, hydrophobic film, uvioresistant film on high temperature resistant matrix such as glass, silicon chip.And adopt the research of sol-gel method load lock layer on the relatively poor packaging film of thermotolerance actually rare in the world, domesticly do not appear in the newspapers as yet.SANG-YUP LEE is a main raw material with polyvinyl alcohol, tetraethoxy and silane coupling agent, on polypropylene film and polyester film, prepared polyvinyl alcohol/silicon-dioxide hybrid inorganic-organic barrier laminated film, but polyvinyl alcohol is to be the synthesized polymer material of main raw material with the oil and natural gas, now, along with increasing the weight of of resource and environmental problem, people more and more pay close attention to natural macromolecular material, especially degradable natural macromolecular material.Chitosan is one of the abundantest natural polymer of content on the earth, is widely used in aspects such as biosensor, organizational project, gas separation membrane and edible film owing to it has degradability, germ resistance, biocompatibility.
Summary of the invention
In view of above-mentioned, the objective of the invention is to propose a kind of method for preparing chitosan/silicon dioxide hybridization barrier packaging composite film.
The method for preparing chitosan/silicon dioxide hybridization barrier packaging composite film of the present invention may further comprise the steps:
(1) the packaging film acid oxidase is handled:
Potassium bichromate, deionized water and the vitriol oil are mixed with mixed solution by mass ratio at 5: 8: 100, and heating in water bath to 50 ℃, again the packaging film that cleans up is put into and wherein carried out acid oxidase and handle after 30 minutes and take out film, wash repeatedly with deionized water earlier, carry out ultrasonic cleaning again, take out, oven dry, standby;
(2) preparation of silicon dioxide gel:
With tetraethoxy and silane coupling agent and ethanol uniform mixing, splash in deionized water and the alcoholic acid mixed solution, the mol ratio of tetraethoxy and silane coupling agent is 7: 1～1: 1, tetraethoxy and silane coupling agent: ethanol: the mol ratio of deionized water is 1: 4: 3, mix after 30 minutes, regulate pH value to 1.5～5, place 30～70 ℃ water bath with thermostatic control then, magnetic agitation is 2～16 hours simultaneously, makes silicon dioxide gel;
(3) preparation of chitosan solution:
It is in 0.5～2% the aqueous hydrochloric acid that chitosan is dissolved in volume ratio, suction filtration, and vacuum defoamation makes mass volume ratio and is 1～2% chitosan solution;
(4) preparation of chitosan/SiO 2 hybrid colloidal sol:
The chitosan solution of above-mentioned preparation is mixed with silicon dioxide gel, wherein the volume percent of chitosan solution is 20～80%, places 30～70 ℃ water bath with thermostatic control to heat, and magnetic agitation is 2～16 hours simultaneously, vacuum defoamation makes chitosan/SiO 2 hybrid colloidal sol;
(5) preparation of laminated film:
The packaging film of handling through acid oxidase is immersed in chitosan/SiO 2 hybrid colloidal sol, adopt dipping-pulling method to film, drying gets chitosan/silicon dioxide hybridization barrier packaging composite film.
Above-mentioned packaging film can be polyolefins (for example new LDPE (film grade), high density polyethylene(HDPE), linear low density polyethylene, polypropylene, Biaxially oriented polypropylene film (BOPP) etc.), polyester (for example polyethylene terephthalate, two-way stretch polyethylene terephthalate, poly-how dioctyl phthalate glycol ester etc.), polyamide-based packaging films commonly used such as (polyamide 6, polyamide 66, two-way stretching polyamides etc.).Drying mode can adopt forced air drying, microwave drying or ultraviolet drying.
The present invention is in dipping-pulling method is filmed, by regulating the thickness of dipping time and pull rate control chitosan/silicon-dioxide hybrid inorganic-organic packaging composite film.
The beneficial effect that the present invention has is:
The present invention is organic phase with the natural polymer chitosan, loading chitosan/silicon-dioxide hybrid inorganic-organic barrier layer on the relatively poor packaging film matrix of thermotolerance, hydridization barrier layer and packaging film close attachment have constituted chitosan/silicon-dioxide hybrid inorganic-organic barrier packaging composite film jointly.Preparation technology is simple, cost is low, adopt sol-gel method, realize the hydridization on chitosan and the silicon dioxide molecules level, form fine and close hybrid inorganic-organic network, add silane coupling agent and improved the attachment fastness of hybrid layer and packaging film, can prevent that hybrid layer from ftractureing or come off.The barrier property of the chitosan/SiO 2 hybrid packaging composite film of the present invention's preparation is significantly increased mechanical property, excellent optical performance.
Embodiment
Below in conjunction with specific examples the present invention is done detailed explanation.
Embodiment 1:
(1) the low-density polyethylene film acid oxidase is handled: potassium bichromate, deionized water and the vitriol oil are mixed with mixed solution with 5: 8: 100 mass ratio, and heating in water bath to 50 ℃, be that 18 microns the low-density polyethylene film that cleans up is put into and wherein carried out acid oxidase and handle again with thickness, after 30 minutes film is taken out, wash repeatedly with deionized water, carry out ultrasonic cleaning again, take out, oven dry, standby;
(2) preparation of silicon dioxide gel: with tetraethoxy and silane coupling agent KH151 and ethanol uniform mixing, splash in deionized water and the alcoholic acid mixed solution, wherein, the mol ratio of tetraethoxy and silane coupling agent KH151 is 7: 1, tetraethoxy and silane coupling agent KH151: ethanol: the mol ratio of deionized water is 1: 4: 3, mixes after 30 minutes, regulate pH value to 1.5 with the vitriol oil, place 30 ℃ water bath with thermostatic control, magnetic agitation is 12 hours simultaneously, makes silicon dioxide gel;
(3) preparation of chitosan solution: it is in 0.5% the aqueous hydrochloric acid that chitosan is dissolved in volume ratio, suction filtration, and vacuum defoamation makes mass volume ratio and is 1% chitosan solution;
(4) preparation of chitosan/SiO 2 hybrid colloidal sol: the chitosan solution of above-mentioned preparation is mixed with silicon dioxide gel, wherein the volume percent of chitosan solution is 20%, place 30 ℃ water bath with thermostatic control to heat, magnetic agitation is 12 hours simultaneously, vacuum defoamation makes chitosan/SiO 2 hybrid colloidal sol;
(5) preparation of laminated film: the low-density polyethylene film of handling through acid oxidase is immersed in chitosan/SiO 2 hybrid colloidal sol, the employing dipping-pulling method is filmed, wet film is put into microwave oven microwave drying, get chitosan/silicon-dioxide hybrid inorganic-organic packaging composite film.
In this hydridization laminated film, the thickness of low-density polyethylene film is 18 microns, and the thickness of hybrid layer is 3 μ m.The oxygen-barrier property of hydridization laminated film is about 40 times of low-density polyethylene film.
Embodiment 2:
(1) the BiOriented Polypropylene Films acid oxidase is handled: potassium bichromate, deionized water, the vitriol oil are mixed with mixed solution with 5: 8: 100 mass ratio, and heating in water bath to 50 ℃, be that 21 microns the BiOriented Polypropylene Films that cleans up is put into and wherein carried out acid oxidase and handle again with thickness, after 30 minutes film is taken out, wash repeatedly with deionized water, carry out ultrasonic cleaning again, take out, oven dry, standby;
(2) preparation of silicon dioxide gel: with tetraethoxy and silane coupling agent KH560 and ethanol uniform mixing, splash in deionized water and the alcoholic acid mixed solution, wherein, the mol ratio of tetraethoxy and silane coupling agent KH560 is 3: 2, tetraethoxy and silane coupling agent KH560: ethanol: the mol ratio of deionized water is 1: 4: 3, mixes after 30 minutes, regulate pH value to 3 with concentrated hydrochloric acid, place 50 ℃ water bath with thermostatic control, magnetic agitation is 8 hours simultaneously, makes silicon dioxide gel;
(3) preparation of chitosan solution: it is in 1% the aqueous hydrochloric acid that chitosan is dissolved in volume ratio, suction filtration, and vacuum defoamation makes mass volume ratio and is 1.5% chitosan solution;
(4) preparation of chitosan/SiO 2 hybrid colloidal sol: the chitosan solution of above-mentioned preparation is mixed with silicon dioxide gel, wherein the volume percent of chitosan solution is 60%, place 50 ℃ water bath with thermostatic control to heat, magnetic agitation is 8 hours simultaneously, vacuum defoamation makes chitosan/SiO 2 hybrid colloidal sol;
(5) preparation of laminated film: the BiOriented Polypropylene Films of handling through acid oxidase is immersed in chitosan/SiO 2 hybrid colloidal sol, the employing dipping-pulling method is filmed, wet film is put into the forced air drying of 80 ℃ of constant temperature air dry ovens, get chitosan/silicon-dioxide hybrid inorganic-organic packaging composite film.
In this hydridization laminated film, BiOriented Polypropylene Films thickness is 21 microns, and hybrid layer thickness is 5 μ m.The oxygen-barrier property of hydridization laminated film is about 100 times of BiOriented Polypropylene Films.
Embodiment 3:
(1) PET (polyethylene terephthalate) polyester film acid oxidase is handled: potassium bichromate, deionized water, the vitriol oil are mixed with mixed solution with 5: 8: 100 mass ratio, and heating in water bath to 50 ℃, be that 50 microns PET polyester films that clean up are put into and wherein carried out acid oxidase and handle again with thickness, after 10 minutes film is taken out, wash repeatedly with deionized water, carry out ultrasonic cleaning again, take out, oven dry, standby;
(2) preparation of silicon dioxide gel: with tetraethoxy and silane coupling agent KH560 and ethanol uniform mixing, splash in deionized water and the alcoholic acid mixed solution, wherein, the mol ratio of tetraethoxy and silane coupling agent KH560 is 1: 1, tetraethoxy and silane coupling agent KH560: ethanol: the mol ratio of deionized water is 1: 4: 3, mixes after 30 minutes, regulate pH value to 5 with concentrated hydrochloric acid, place 70 ℃ water bath with thermostatic control, magnetic agitation is 4 hours simultaneously, makes silicon dioxide gel;
(3) preparation of chitosan solution: it is in 1% the aqueous hydrochloric acid that chitosan is dissolved in volume ratio, suction filtration, and vacuum defoamation makes mass volume ratio and is 2% chitosan solution;
(4) preparation of chitosan/SiO 2 hybrid colloidal sol: the chitosan solution of above-mentioned preparation is mixed with silicon dioxide gel, wherein the volume percent of chitosan solution is 80%, place 70 ℃ water bath with thermostatic control to heat, magnetic agitation is 4 hours simultaneously, vacuum defoamation makes chitosan/SiO 2 hybrid colloidal sol;
(5) preparation of laminated film: the PET polyester film of handling through acid oxidase is immersed in chitosan/SiO 2 hybrid colloidal sol, the employing dipping-pulling method is filmed, with wet film ultraviolet drying under ultra violet lamp, get chitosan/silicon-dioxide hybrid inorganic-organic packaging composite film.
In this hydridization laminated film, PET polyester film thickness is 50 microns, and hybrid layer thickness is 8 μ m.The oxygen-barrier property of hydridization laminated film is about 80 times of PET polyester film.
Claims (2)
1. prepare the method for chitosan/silicon dioxide hybridization barrier packaging composite film, may further comprise the steps:
(1) the packaging film acid oxidase is handled:
Potassium bichromate, deionized water and the vitriol oil are mixed with mixed solution by mass ratio at 5: 8: 100, and heating in water bath to 50 ℃, again the packaging film that cleans up is put into and wherein carried out acid oxidase and handle after 30 minutes and take out film, wash repeatedly with deionized water earlier, carry out ultrasonic cleaning again, take out, oven dry, standby;
(2) preparation of silicon dioxide gel:
With tetraethoxy and silane coupling agent and ethanol uniform mixing, splash in deionized water and the alcoholic acid mixed solution, the mol ratio of tetraethoxy and silane coupling agent is 7: 1～1: 1, tetraethoxy and silane coupling agent: ethanol: the mol ratio of deionized water is 1: 4: 3, mix after 30 minutes, regulate pH value to 1.5～5, place 30～70 ℃ water bath with thermostatic control then, magnetic agitation is 2～16 hours simultaneously, makes silicon dioxide gel;
(3) preparation of chitosan solution:
It is in 0.5～2% the aqueous hydrochloric acid that chitosan is dissolved in volume ratio, suction filtration, and vacuum defoamation makes mass volume ratio and is 1～2% chitosan solution;
(4) preparation of chitosan/SiO 2 hybrid colloidal sol:
The chitosan solution of above-mentioned preparation is mixed with silicon dioxide gel, wherein the volume percent of chitosan solution is 20～80%, places 30～70 ℃ water bath with thermostatic control to heat, and magnetic agitation is 2～16 hours simultaneously, vacuum defoamation makes chitosan/SiO 2 hybrid colloidal sol;
(5) preparation of laminated film:
The packaging film of handling through acid oxidase is immersed in chitosan/SiO 2 hybrid colloidal sol, adopt dipping-pulling method to film, drying gets chitosan/silicon dioxide hybridization barrier packaging composite film.
2. the method for preparing chitosan/silicon dioxide hybridization barrier packaging composite film according to claim 1 is characterized in that packaging film is polyolefins, polyester or polyamide-based packaging film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910153634XA CN101671445B (en) | 2009-09-30 | 2009-09-30 | Method for preparing chitosan/silicon dioxide hybridization barrier packaging composite film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910153634XA CN101671445B (en) | 2009-09-30 | 2009-09-30 | Method for preparing chitosan/silicon dioxide hybridization barrier packaging composite film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101671445A CN101671445A (en) | 2010-03-17 |
| CN101671445B true CN101671445B (en) | 2011-06-15 |
Family
ID=42018875
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910153634XA Expired - Fee Related CN101671445B (en) | 2009-09-30 | 2009-09-30 | Method for preparing chitosan/silicon dioxide hybridization barrier packaging composite film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101671445B (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051611B (en) * | 2010-12-31 | 2012-07-11 | 大连工业大学 | Metal surface treating agent |
| CN102100923B (en) * | 2011-01-21 | 2013-08-14 | 陕西师范大学 | Preparation method of micron Ag2O2 doped chitosan hydrogel antibacterial auxiliary material |
| CN102964983B (en) * | 2012-12-12 | 2015-01-07 | 广州市高士实业有限公司 | Silicon hybrid composite coating electronic adhesive and preparation method thereof |
| CN103094612B (en) * | 2013-02-04 | 2015-10-07 | 江苏科技大学 | Containing lithium Ludox doping PVDF composite gel polymer electrolyte film and preparation method |
| CN103168827B (en) * | 2013-04-01 | 2014-08-06 | 肇庆学院 | Method for preparing freshness-retaining film through Maillard reaction of collagen and chitosan |
| CN104014316B (en) * | 2014-06-10 | 2016-01-20 | 陕西科技大学 | The method of tannic acid in the preparation of chitosan magnetic and adsorbed water |
| CN104233273A (en) * | 2014-09-26 | 2014-12-24 | 山东大学 | Chromium-free silicon passivation solution for passivating aluminum or aluminum alloy surface as well as preparation and using methods |
| CN104862992A (en) * | 2015-06-05 | 2015-08-26 | 四川大学 | Chitosan hybrid silica solution leather dyeing assistant and preparation method thereof |
| CN106311157A (en) * | 2016-08-31 | 2017-01-11 | 安徽东锦服饰有限公司 | Preparation method of composite film with adsorption function |
| CN106883565B (en) * | 2017-03-29 | 2019-04-26 | 汕头市岐山橡胶塑料有限公司 | A kind of high-barrier composite film |
| CN106963980B (en) * | 2017-04-17 | 2020-01-14 | 华南理工大学 | Preparation method and application of chitosan-silicon dioxide nano hybrid material |
| CN107376665A (en) * | 2017-09-13 | 2017-11-24 | 合肥学院 | A kind of preparation method of chitosan-based organic inorganic hybridization porous membrane |
| CN109745951B (en) * | 2019-01-24 | 2022-04-26 | 浙江理工大学 | Preparation method of MOF polypropylene composite material with magnetic response |
| CN110003627B (en) * | 2019-04-04 | 2021-01-19 | 苏州思达奇环保新材料有限公司 | Degradable solid electrolyte membrane, preparation method thereof and lithium battery prepared from degradable solid electrolyte membrane |
| CN111019171B (en) * | 2019-12-27 | 2021-04-27 | 福州大学 | Preparation method of antibacterial barrier PET (polyethylene terephthalate) protective film prepared by doping modified aluminosilicate with carboxylated chitosan |
| CN114524961A (en) * | 2021-12-30 | 2022-05-24 | 巨鑫(江苏)新材料包装有限公司 | Microwave-refrigeratable functional SiO2Coating PP composite membrane material and preparation process thereof |
| CN114477783A (en) * | 2022-01-14 | 2022-05-13 | 中山爱因新材料有限公司 | Composite material and preparation method and application thereof |
-
2009
- 2009-09-30 CN CN200910153634XA patent/CN101671445B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101671445A (en) | 2010-03-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101671445B (en) | Method for preparing chitosan/silicon dioxide hybridization barrier packaging composite film | |
| US9982140B2 (en) | Inorganic-organic hybrid oxide polymer and manufacturing method thereof | |
| JP5880238B2 (en) | LAMINATE MEMBER, MANUFACTURING METHOD THEREOF, AND LAMINATE | |
| Chaudhri et al. | Fabrication of efficient pervaporation desalination membrane by reinforcement of poly (vinyl alcohol)–silica film on porous polysulfone hollow fiber | |
| JP2011173261A (en) | Gas-barrier film and method for producing the same | |
| Islam et al. | Preparation and characterization of crack-free sol–gel based SiO 2–TiO 2 hybrid nanoparticle film | |
| KR20110098960A (en) | High-barrier composites and method for the production thereof | |
| Gokhale et al. | Recent advances in the fabrication of nanostructured barrier films | |
| KR20140079813A (en) | Composite structure, packaging material and molded article using same, and production method and coating liquid therefor | |
| CN102718410A (en) | Method for preparing self-cleaning antifogging coating film | |
| KR20160095615A (en) | Oxygen enrichment membrane and method for producing same | |
| TWI658940B (en) | Antistatic sheet and packaging material and electronic device containing the same | |
| JP3951264B2 (en) | Transparent moisture-resistant gas barrier film | |
| CN1638953A (en) | Gas barrier material | |
| KR19990088561A (en) | Gas-barrier laminate film and method for producing same | |
| JP2004217766A (en) | Gas-barrier composition and gas-barrier film using the same | |
| Zhao et al. | Effects of HPC on the microstructure and hydrophilicity of sol–gel-derived TiO2 films | |
| CN101544771B (en) | High-sequential inorganic substance patterning and preparation method thereof | |
| JP4065266B2 (en) | Gas barrier film and method for producing the same | |
| JP5201073B2 (en) | Transparent gas barrier film | |
| JP2005046668A (en) | Fluid separating filter and its manufacturing method | |
| WO2007042993A2 (en) | A laminated material having a high oxygen-barrier effect | |
| JP2007090663A (en) | Gas barrier laminated body | |
| JP5270084B2 (en) | Moisture-proof composition and moisture-proof sheet using the same | |
| Figueira | Greener synthesis and applications of hybrid sol–gel-processed materials |
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 |
Granted publication date: 20110615 Termination date: 20140930 |
|
| EXPY | Termination of patent right or utility model |