CN104893197A - Preparation method of water-resistant composite film with polyvinyl alcohol/silver loaded oxidized cellulose - Google Patents
Preparation method of water-resistant composite film with polyvinyl alcohol/silver loaded oxidized cellulose Download PDFInfo
- Publication number
- CN104893197A CN104893197A CN201510132044.4A CN201510132044A CN104893197A CN 104893197 A CN104893197 A CN 104893197A CN 201510132044 A CN201510132044 A CN 201510132044A CN 104893197 A CN104893197 A CN 104893197A
- Authority
- CN
- China
- Prior art keywords
- surgicel
- preparation
- polyvinyl alcohol
- water
- film
- 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.)
- Granted
Links
Abstract
The invention relates to a preparation method of a water-resistant composite film with polyvinyl alcohol/silver loaded oxidized cellulose, and particularly to a water-resistant composite material in which nano silver particles, and belongs to the field of polymer materials and biological materials. According to the invention, silver loaded oxidized cellulose is added into a polyvinyl alcohol solution; and the water-resistant composite film with polyvinyl alcohol/silver loaded oxidized cellulose is obtained through intermolecular forces and effects of secondary valence bonds and polyvinyl alcohol. The composite film is good in water resistance, thermal stability and antibacterial property and has a broad application prospect in the field of packaging materials and in medicine.
Description
Technical field
The present invention relates to the preparation method of the SURGICEL composite membrane of a kind of water-resistant polyvinyl alcohol/load silver, particularly add nano-Ag particles to water tolerance matrix material, belong to macromolecular material and technical field of biological material.
Background technology
Water miscible polyvinyl alcohol (PVA) is hydrolyzed by Vinyl Acetate Copolymer and obtains, and structural formula is-CH2CH (OH)
n-be a kind of hydroxyl high molecular polymer.PVA molecular backbone chain is carbochain, and containing a hydroxyl on each repeating unit, because hydroxyl size is little, polarity is strong, easily forms hydrogen bond, and its stable chemical nature has enough thermostabilitys, the wetting ability of height and water-soluble; Simultaneously it also has good film-forming properties and bonding force, has remarkable grease resistance and solvent resistance and good physical and chemical stability, is widely used in the infiltration evaporation membrane process dewatered.Containing great amount of hydroxy group on PVA molecular chain, make hydrogen bond very strong with intermolecular existence in molecule, therefore have highly crystalline, making the ventilation property of PVA very little, is the high-barrier packaging material of excellent property.But a large amount of existence of hydroxyl, result also in PVA and there is water-fast, the shortcoming such as poor heat resistance and creep, make PVA film water-fast, high temperature resistant and large to components permeate flux separated in mixture, selectivity is high, need to carry out blended or chemical modification process to it.
Because PVA wetting ability is higher, when ambient moisture is larger, hydroxyl easily and water molecules formation hydrogen bond, PVA aggregated structure is caused to change, its barrier is sharply declined, limits the application in a lot of field, particularly the application of daily wrapping material aspect.So, water tolerance modification need be carried out to PVA, reduce humidity to the impact of PVA barrier property.PVA water tolerance mechanism of modification makes the hydroxyl on PVA molecular chain all or part of closed by chemistry or physical method, can reduce its wetting ability, reach the object improving water tolerance.The method of current raising water tolerance mainly contains water-proof coating method, blending method and crosslinking etc.At present conventional properties-correcting agent has aldehydes, boric acid, urea, organosilicon radical etc., but these properties-correcting agent or there is toxicity or react restive.
Mierocrystalline cellulose is very wide in occurring in nature distribution, is the main component forming plant.In vegitabilia, cellulosic total amount about reaches 26 × 1011 tons.According to estimates, the whole world every year can production of cellulose 1,000 hundred million tons, but only has 2,000,000 tons of Mierocrystalline celluloses to produce for cellulosic fibre at present, accounts for 0.2% of ultimate production.The current major part of cellulose resource fails to be used effectively.Therefore, exploitation Mierocrystalline cellulose, is applied to the Sustainable development to human society of novel material, new forms of energy and new technical field and is had great importance.
Summary of the invention
The object of the invention is the SURGICEL adding load silver in PVA, reduce the cost of PVA based composites, strengthen the water tolerance of PVA based composites, in addition, in PVA/ cellulose composite material, add silver, silver can produce very strong hydrogen bond action with PVA matrix; In addition, silver has good physicochemical property, can expand the application of composite membrane in medical science and electricity.
The object of the invention is to be achieved through the following technical solutions: the preparation method of the SURGICEL composite membrane of a kind of water-resistant polyvinyl alcohol/load silver, comprises following step:
(1) preparation of SURGICEL film: get 8.76g LiOH, 12g urea, 79.24g water is mixed solvent, add 5g Mierocrystalline cellulose, stir and be placed on cryogenic freezing 24h in refrigerator; Cellulose solution after freezing is thawed, after mechanical stirring makes it be good flow shape, at 4 DEG C, with the centrifugal 10min bubble removing of 8000r/min, by the solution after centrifugal on a glass, certain thickness is pushed into, freezing film in the solidification liquid of the sodium bisulfate aqueous solution; Obtained film is soaked in deionized water and washs, solidification liquid is cleaned; Clean film is cut to fixed size, soaks 4h with in the ethanolic soln of 30%, 50%, 70%, 90%, 100% successively, removed the water in cellulose membrane.
(2) the SURGICEL film preparation of load silver: the SURGICEL film of taking periodate oxidation certain hour is placed in certain density silver ammino solution and reacts 20min, obtains the SURGICEL film of load silver.
(3) preparation of the SURGICEL composite membrane of polyvinyl alcohol/load silver: the cellulose membrane that above-mentioned steps (2) obtains is shredded, and with PVA adds deionized water with certain proportion and puts into there-necked flask and react 1h under mechanical stirring, then the solution in flask to be poured in mould into 40 DEG C of evaporating solvent 24h in baking oven shaping.
According to the preparation method of the SURGICEL composite membrane of preceding claim polyvinyl alcohol/load silver, it is characterized in that Periodic acid concentration described in step (2) is 0.1-0.9mol/L oxidization time 0-48h.
According to the preparation method of the SURGICEL composite membrane of preceding claim polyvinyl alcohol/load silver, it is characterized in that in step (2), silver ammino solution concentration is 0.01-0.09mol/L.
According to the preparation method of the SURGICEL composite membrane of preceding claim polyvinyl alcohol/load silver, it is characterized in that PVA in claim steps (3): the cellulosefilm mass ratio of load silver is 5:1-5:5.
Compared with prior art, tool of the present invention has the following advantages and beneficial effect: PVA molecular chain contains great amount of hydroxy group (-OH) and hydrogen bond, make it have good water-soluble, hydrogen bond crosslinks can be passed through with natural polymer, compact siro spinning technology, the cellulosefilm adding load silver again obtains composite membrane, strengthens mechanical property and processing characteristics, the water tolerance of macromolecular material.Modified this composite membrane of PVA matrix material has water tolerance and thermostability and germ resistance, makes its application in biodegradable wrapping material field and medical science become possibility.
Accompanying drawing illustrates:
Fig. 1 is Fourier infrared spectrum (FTIR) figure of embodiment composite membrane.。
Fig. 2 and Fig. 3 is composite membrane TGA test pattern in embodiment 1.
Embodiment
In order to explain the present invention better, below in conjunction with specific embodiment, the present invention is further explained in detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) cellulose membrane preparation: configuration cellulose solution, LiOH8.76g, urea 12g, water 79.24g, Mierocrystalline cellulose 5g, stir and be placed on cryogenic freezing 24h in refrigerator.Cellulose solution after freezing is thawed, centrifugal after mechanical stirring makes it be good flow shape (4 DEG C, 8,000r/min, 10min), solution after centrifugal is made film, and solidification liquid is the sodium bisulfate aqueous solution, is soaked in deionized water by obtained film and washs, solidification liquid is cleaned, clean film is cut to fixed size, soaks 4h with in the ethanolic soln of 30%, 50%, 70%, 90%, 100% successively, removed the water in cellulose membrane.
(2) cellulose membrane oxidation: the preparation 0.1g/ml Periodic acid aqueous solution, cellulosefilm is immersed in Periodic acid solution, under lucifuge room temperature, react 24h, 36h, 48h, take out the cellulosefilm of oxidation, use deionized water repetitive scrubbing, at least three times. film is put into acetone and soaks 24h.Obtain the tunica fibrosa of different oxidization time is designated as C24, C36, C48 respectively.
(3) silver ammino solution and SURGICEL film reaction: the silver nitrate solution adding 2ml 2% in the test tube of cleaning, then tube shaken limit in limit dropwise adds the weak ammonia of 2%, to the initial precipitation produced is dissolved just.Now silver ammino solution concentration is 0.1mol/L, then is 0.01mol/L by silver ammino solution dilution.Join in 50ml 0.01mol/L silver ammino solution by a certain amount of different oxidization time SURGICEL film, lucifuge room temperature reaction 20min, the cellulose membrane obtaining surface attachment silver simple substance is designated as CAg24, CAg36, CAg48 respectively.
(4) the surface attachment silver cellulose membrane of simple substance and PVA compound: the CAg film getting 4 groups of 0.2g respectively shreds, get 1gPVA simultaneously, film and PVA are put into there-necked flask, add 15ml water, after 95 DEG C of oil bath reactions 1h, 1h, reacted solution is poured in mould, after cooling, put into baking oven 40 DEG C of evaporating solvent 24h film forming.
Embodiment 2
Thermogravimetric analyzer (TGA) be TGA/1100SF in a nitrogen atmosphere temperature rise rate be use under 15 DEG C/min, temperature range is 25-600 DEG C, test pure PVA film (a), PVA/CAg24 (b), PVA/CAg36 (c) and PVA/CAg48 (d) respectively, each sample about employs 8-10mg.Obtain thermogravimetric curve Fig. 2 and DTG Fig. 3 of composite membrane etc.
Can see that the temperature of initial decomposition of PVA is higher from Fig. 2 thermogravimetric curve, be 208 DEG C, after adding CAg, and the temperature of initial decomposition of composite film material declines, and have decreased to about 145 DEG C, decline has appearred in thermostability.After wherein adding CAg48, the residual quantity obtained is maximum, and the residual quantity of other three groups of samples is more or less the same.Can see that from Fig. 3 the main decomposition temperature of PVA is at 265 DEG C, after adding CAg, the main decomposition of composite membrane has risen to 330 DEG C.
Claims (4)
1. a preparation method for the SURGICEL composite membrane of water-resistant polyvinyl alcohol/load silver, is characterized in that carrying out according to following steps:
(1) preparation of SURGICEL film: get 8.76g LiOH, 12g urea, 79.24g water is mixed solvent, add 5g Mierocrystalline cellulose, stir and be placed on cryogenic freezing 24h in refrigerator; Cellulose solution after freezing is thawed, after mechanical stirring makes it be good flow shape, at 4 DEG C, with the centrifugal 10min bubble removing of 8000r/min, by the solution after centrifugal on a glass, certain thickness is pushed into, freezing film in the solidification liquid of the sodium bisulfate aqueous solution; Obtained film is soaked in deionized water and washs, solidification liquid is cleaned; Clean film is cut to fixed size, soaks 4h with in the ethanolic soln of 30%, 50%, 70%, 90%, 100% successively, removed the water in cellulose membrane.
(2) the SURGICEL film preparation of load silver: the SURGICEL film of taking periodate oxidation certain hour is placed in certain density silver ammino solution and reacts 20min, obtains the SURGICEL film of load silver.
(3) preparation of the SURGICEL composite membrane of polyvinyl alcohol/load silver: the cellulose membrane that above-mentioned steps (2) obtains is shredded, and with PVA adds deionized water with certain proportion and puts into there-necked flask and react 1h under mechanical stirring, then the solution in flask to be poured in mould into 40 DEG C of evaporating solvent 24h in baking oven shaping.
2., according to the preparation method of the SURGICEL composite membrane of preceding claim polyvinyl alcohol/load silver, it is characterized in that Periodic acid concentration described in step (2) is 0.1-0.9mol/L oxidization time 0-48h.
3., according to the preparation method of the SURGICEL composite membrane of preceding claim polyvinyl alcohol/load silver, it is characterized in that in step (2), silver ammino solution concentration is 0.01-0.09mol/L.
4., according to the preparation method of the SURGICEL composite membrane of preceding claim polyvinyl alcohol/load silver, it is characterized in that PVA in claim steps (3): the cellulosefilm mass ratio of load silver is 5:1-5:5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510132044.4A CN104893197B (en) | 2015-03-24 | 2015-03-24 | A kind of preparation method of the oxycellulose composite membrane of water-resistant polyvinyl alcohol/load silver |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510132044.4A CN104893197B (en) | 2015-03-24 | 2015-03-24 | A kind of preparation method of the oxycellulose composite membrane of water-resistant polyvinyl alcohol/load silver |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104893197A true CN104893197A (en) | 2015-09-09 |
| CN104893197B CN104893197B (en) | 2016-10-05 |
Family
ID=54026187
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510132044.4A Active CN104893197B (en) | 2015-03-24 | 2015-03-24 | A kind of preparation method of the oxycellulose composite membrane of water-resistant polyvinyl alcohol/load silver |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104893197B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418976A (en) * | 2015-12-21 | 2016-03-23 | 郑裕东 | Phototransformation antibacterial particle-modified functional bacterial cellulose compound sol and preparation of composite material |
| CN105442307A (en) * | 2015-12-16 | 2016-03-30 | 厦门大学 | Preparation method of nanosilver-supported antibiotic fibers |
| CN106366349A (en) * | 2016-08-29 | 2017-02-01 | 昆明理工大学 | Preparation method for corncob micron fiber-reinforced oxycellulose/polyvinyl alcohol blending mulching film |
| CN110144093A (en) * | 2019-05-14 | 2019-08-20 | 西安理工大学 | A kind of preparation method of nano silver/cellulose/polyvinyl alcohol laminated film |
| CN112111119A (en) * | 2020-09-21 | 2020-12-22 | 桂林理工大学 | Polyvinyl alcohol nanocomposite with excellent performance and preparation method thereof |
| CN113072727A (en) * | 2021-05-10 | 2021-07-06 | 陕西科技大学 | Preparation method of AgNWs nano particle-cholesteric liquid crystal composite film |
| CN114805870A (en) * | 2022-03-11 | 2022-07-29 | 安徽农业大学 | Water-resistant self-healing polyvinyl alcohol-based composite film and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4926504A (en) * | 1972-07-06 | 1974-03-09 | ||
| US3932564A (en) * | 1972-05-15 | 1976-01-13 | Monsanto Company | Electroconductive resins and process of preparation |
| EP0039854A2 (en) * | 1980-05-09 | 1981-11-18 | Hoechst Aktiengesellschaft | Polyvinyl alcohol composition, its preparation process, its use |
| JPS60184489A (en) * | 1984-03-02 | 1985-09-19 | S D K Kk | Production of flux-bound hard solder |
| JPH0926504A (en) * | 1995-05-11 | 1997-01-28 | Fuji Photo Film Co Ltd | Production of optical film and apparatus for production therefor |
| CN101444636A (en) * | 2009-01-05 | 2009-06-03 | 北京化工大学 | Degradable multiporous faecula/PVA biological film and preparation method thereof |
| CN103613773A (en) * | 2013-11-07 | 2014-03-05 | 常州大学 | Preparation method of flexible transparent conducting polymer thin film with antibacterial properties |
-
2015
- 2015-03-24 CN CN201510132044.4A patent/CN104893197B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3932564A (en) * | 1972-05-15 | 1976-01-13 | Monsanto Company | Electroconductive resins and process of preparation |
| JPS4926504A (en) * | 1972-07-06 | 1974-03-09 | ||
| EP0039854A2 (en) * | 1980-05-09 | 1981-11-18 | Hoechst Aktiengesellschaft | Polyvinyl alcohol composition, its preparation process, its use |
| JPS60184489A (en) * | 1984-03-02 | 1985-09-19 | S D K Kk | Production of flux-bound hard solder |
| JPH0926504A (en) * | 1995-05-11 | 1997-01-28 | Fuji Photo Film Co Ltd | Production of optical film and apparatus for production therefor |
| CN101444636A (en) * | 2009-01-05 | 2009-06-03 | 北京化工大学 | Degradable multiporous faecula/PVA biological film and preparation method thereof |
| CN103613773A (en) * | 2013-11-07 | 2014-03-05 | 常州大学 | Preparation method of flexible transparent conducting polymer thin film with antibacterial properties |
Non-Patent Citations (2)
| Title |
|---|
| 冯军强 等: "Ag/PVA纳米聚合物复合材料的制备及其电性能研究", 《中国电机工程学报》 * |
| 庄旭品 等: "聚乙烯醇-纳米银复合膜的制备及表征", 《塑料工业》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105442307A (en) * | 2015-12-16 | 2016-03-30 | 厦门大学 | Preparation method of nanosilver-supported antibiotic fibers |
| CN105442307B (en) * | 2015-12-16 | 2017-07-04 | 厦门大学 | A kind of preparation method of loading nano silvery anti-bacterial fibre |
| CN105418976A (en) * | 2015-12-21 | 2016-03-23 | 郑裕东 | Phototransformation antibacterial particle-modified functional bacterial cellulose compound sol and preparation of composite material |
| CN105418976B (en) * | 2015-12-21 | 2018-04-13 | 郑裕东 | A kind of preparation of light conversion antimicrobial particle rhetorical function bacteria cellulose compounding colloidal sol and composite material |
| CN106366349A (en) * | 2016-08-29 | 2017-02-01 | 昆明理工大学 | Preparation method for corncob micron fiber-reinforced oxycellulose/polyvinyl alcohol blending mulching film |
| CN106366349B (en) * | 2016-08-29 | 2018-11-09 | 昆明理工大学 | Corncob micrometer fibers enhance the preparation method of oxycellulose/polyvinyl alcohol blending mulch |
| CN110144093A (en) * | 2019-05-14 | 2019-08-20 | 西安理工大学 | A kind of preparation method of nano silver/cellulose/polyvinyl alcohol laminated film |
| CN110144093B (en) * | 2019-05-14 | 2022-04-12 | 西安理工大学 | Preparation method of nano-silver/cellulose/polyvinyl alcohol composite film |
| CN112111119A (en) * | 2020-09-21 | 2020-12-22 | 桂林理工大学 | Polyvinyl alcohol nanocomposite with excellent performance and preparation method thereof |
| CN113072727A (en) * | 2021-05-10 | 2021-07-06 | 陕西科技大学 | Preparation method of AgNWs nano particle-cholesteric liquid crystal composite film |
| CN114805870A (en) * | 2022-03-11 | 2022-07-29 | 安徽农业大学 | Water-resistant self-healing polyvinyl alcohol-based composite film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104893197B (en) | 2016-10-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104893197A (en) | Preparation method of water-resistant composite film with polyvinyl alcohol/silver loaded oxidized cellulose | |
| CN105884576B (en) | A kind of CuZn bimetallic organic framework material is the copper-based catalysts and its preparation method and application of presoma | |
| CN104174388B (en) | A kind of metal organic frame composite and preparation method thereof | |
| CN102489716B (en) | Preparation method for lignosulfonate nano-silver colloid | |
| CN110026097B (en) | Preparation method of PIM-1@ MOFs/polymer composite pervaporation membrane | |
| CN102068925B (en) | Preparation method of polyaniline nano composite film | |
| CN105542227A (en) | Carbon fiber reinforcement and preparation method thereof | |
| CN109589917B (en) | Solid phase micro-extraction fiber based on double-layer hollow zinc oxide/carbon material and preparation method thereof | |
| CN109701361A (en) | For absorbing SO2And NO2Polyalcohol-choline eutectic solvent and preparation method | |
| CN109865439A (en) | A kind of mixed substrate membrane containing nano-grade molecular sieve and preparation method and application of the filling of ZIF-8/ graphite phase carbon nitride | |
| CN103170260B (en) | Modified nanometer titanium dioxide based preparation process of hollow ultrafiltration membrane fiber | |
| CN109749108A (en) | A kind of edible tapioca composite package film and its preparation method and application | |
| CN106930100A (en) | A kind of preparation method of polyimides/graphene oxide complex fiber material | |
| CN103394295A (en) | Hydrophilic PVDF (Polyvinylidene Fluoride) composite ultrafiltration membrane and preparation method thereof | |
| CN104300164A (en) | Preparation method for complex proton exchange membrane | |
| CN113209841A (en) | Mixed matrix membrane of aminated ZIF-8 and polyvinyl alcohol and preparation method and application thereof | |
| CN107955418A (en) | A kind of hydrophobic galapectite based on catechol chemical modification and preparation method thereof | |
| CN111617645A (en) | Preparation method of low-resistance high-selectivity mixed matrix membrane based on hollow MOFs (metal-organic frameworks) material | |
| CN112675720A (en) | Preparation method and application of mixed matrix membrane filled with bimetallic strip material | |
| CN110563990A (en) | Preparation method and application of silver-containing cellulose composite material with photodegradation function | |
| CN109134944A (en) | A kind of porous small ball and its application with different chemical functional groups | |
| CN105664850B (en) | A kind of preparation method and applications of high performance carbon base carbon dioxide sorbing material | |
| CN111995799B (en) | Preparation method of nano-silver/cellulose composite antibacterial material | |
| CN101891936A (en) | Preparation method of composite material based on epoxy resin and phosphazene nanotubes | |
| CN102093717A (en) | Sulfonated polyethersulfone/TiO2 nano composite material 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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200331 Address after: 313000 Room 1403, 14th Floor, Building B, Freeport, Headquarters 1188 District Fulu Road, Wuxing District, Huzhou City, Zhejiang Province Patentee after: Zhejiang creation Intellectual Property Service Co.,Ltd. Address before: No. 1800 road 214122 Jiangsu Lihu Binhu District City of Wuxi Province Patentee before: Jiangnan University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200608 Address after: Room 501, Office Building of Market Supervision Bureau of Langchuan Avenue, Jianping Town, Langxi County, Xuancheng City, Anhui Province Patentee after: Langxi pinxu Technology Development Co., Ltd Address before: 313000 Room 1403, 14th Floor, Building B, Freeport, Headquarters 1188 District Fulu Road, Wuxing District, Huzhou City, Zhejiang Province Patentee before: Zhejiang creation Intellectual Property Service Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211011 Address after: 201508 No. 288, Shanfu West Road, Shanyang Town, Jinshan District, Shanghai Patentee after: SHANGHAI BAIXIN NEW MATERIAL TECHNOLOGY Co.,Ltd. Address before: Room 501, office building, Langchuan Avenue, Jianping Town, Langxi County, Xuancheng City, Anhui Province Patentee before: Langxi pinxu Technology Development Co., Ltd |
|
| TR01 | Transfer of patent right |