CN103131033B - Method for preparing nano manganese dioxide/nano microcrystalline cellulose composite films - Google Patents
Method for preparing nano manganese dioxide/nano microcrystalline cellulose composite films Download PDFInfo
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- CN103131033B CN103131033B CN201310089398.6A CN201310089398A CN103131033B CN 103131033 B CN103131033 B CN 103131033B CN 201310089398 A CN201310089398 A CN 201310089398A CN 103131033 B CN103131033 B CN 103131033B
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Abstract
The invention discloses a method for preparing nano manganese dioxide/nano microcrystalline cellulose composite films. According to the method, the nano manganese dioxide/nano microcrystalline cellulose composite films which have excellent mechanical properties and the functions of light, heat, electromagnetism and the like are prepared in one step in a manner that nano-cellulose colloidal suspension with stable nature is prepared from waste loofah sponge, is used as a matrix and is subjected to in-situ composite reaction with potassium permanganate liquid with strong oxidability.
Description
Technical field
The invention belongs to hybridized nano composite material preparation and application technical field, be specifically related to a kind of method preparing nano-manganese dioxide/nano micro crystal cellulose laminated film.
Background technology
Mierocrystalline cellulose is biodegradable, reproducible natural macromolecular material the abundantest in the world, and plant by photosynthesis, can produce the Mierocrystalline cellulose of hundreds of millions tons every year.Crystalline state nano-cellulose is the structural support of natural cellulose matrix material, from natural cellulose, isolate nano-cellulose, and consequent nanoscale effect makes it have superior mechanical property.Nano-cellulose molecule and supramolecular aggregation thereof is manipulated in the multiple dimensioned scope of micro-nano, formulate out the new nanometer fine chemical product with excellent function, new nano material further thus, become Disciplinary Frontiers and the tackling key problem focus of Cellulose Science research at present.
Although inorganic nano material chemical constitution flexibly adjustable, functional performance enrich, usually lack supramolecular aggregation or other organic macromolecule structure diversities and easy processing forming.Nano-cellulose is as a kind of novel Bio-Nano-Materials, the a large amount of active reaction sites in its higher specific surface area, meticulous tridimensional nano net structure and surface can be used as " biological template agent " and uses, to obtaining the controlled and nano composite material be evenly distributed of pattern, size.With nano-inorganic substance, NCC is adulterated, nano-cellulose not only can be made to obtain more excellent mechanical property, the functions such as more abundant optical, electrical, the magnetic of NCC, absorption, catalysis can be given simultaneously.Therefore, this novel biomaterial of nano-cellulose and various functional inorganic nanophase are carried out compound, and the product innovation of generation and New function cannot be estimated.To sum up, carry out controlled synthesis and the performance study of functional type nano-inorganic substance/nano-cellulose matrix material, for the applied research of promotion nano-cellulose in new technology, novel material and new forms of energy, there is important scientific meaning.Take potassium permanganate as oxygenant, the nano-cellulose soliquid utilizing discarded Vegetable Sponge of Luffa obtained be stablizer, template and reductive agent, original position prepares the correlative study of nano-manganese dioxide/nano micro crystal cellulose laminated film, and there is not been reported.
Summary of the invention
The object of the present invention is to provide a kind of method preparing nano-manganese dioxide/nano micro crystal cellulose laminated film, it is that one utilizes natural discarded Vegetable Sponge of Luffa as raw material, adopts gentle condition to prepare the method for nano-manganese dioxide/nano micro crystal cellulose laminated film.The method be utilize that nano-cellulose soliquid is stablizer, template and reductive agent, potassium permanganate is oxygenant, one step original position prepares nano-manganese dioxide/nano micro crystal cellulose laminated film, is a kind of good mechanical performance and has the matrix material of the functions such as light, heat, electromagnetism concurrently.
For achieving the above object, the present invention adopts following technical scheme:
A kind of method preparing nano-manganese dioxide/nano micro crystal cellulose laminated film comprises the following steps:
(1) discarded Vegetable Sponge of Luffa raw material is cleaned, naturally dry, pulverize, cross 40 mesh sieves, after 105 ~ 110 DEG C of oven dry 12 ~ 24h to constant weight, be placed in moisture eliminator for subsequent use with sealing bag encapsulation;
(2) luffa vegetable sponge described in step (1) is placed in apparatus,Soxhlet's, with benzene alcoholic solution extracting 5 ~ 8 h at 80 ~ 100 DEG C, with Textone 65 ~ 85 DEG C of process 6 ~ 9h in acid condition, with massfraction be 1 ~ 6% potassium hydroxide solution at 80 ~ 100 DEG C, process 3 ~ 5h, be hydrochloric acid reprocessing 1 ~ 3h at 70 ~ 90 DEG C of 0.5 ~ 2% with massfraction, cooling, is washed till neutrality with deionized water, obtain Microcrystalline Cellulose powder after carrying out lyophilize again, it is for subsequent use that collection is placed in moisture eliminator;
(3) by the Microcrystalline Cellulose powder described in step (2) and massfraction be the sulphuric acid soln hybrid reaction 30 ~ 60min of 64 %, centrifugal, dialysis, concentrated, i.e. obtained nano-cellulose soliquid;
(4) dialyse after the nano-cellulose soliquid described in step (3) being mixed ultrasonic 1 ~ 6h with potassium permanganate solution, until the no change of the color of dialyzate, obtained nano-manganese dioxide/Nanocrystalline Cellulose Colloid mixture, be placed on again in culture dish, spontaneous evaporation a couple of days, obtain nano-manganese dioxide/nano micro crystal cellulose laminated film.
Benzene alcoholic solution described in step (2) is benzene-alcohol mixeding liquid, and its volume ratio is 1.5 ~ 2.5:1.
Acidic conditions described in step (2) is pH=4 ~ 5, adopts Glacial acetic acid to regulate.
The quality of the Microcrystalline Cellulose powder described in step (3) and the volume ratio of sulfuric acid are 1 g:8 ~ 12mL.
Hybrid reaction temperature described in step (3) is 30 ~ 60 DEG C.
Concentrated rear obtained nano-cellulose colloidal suspension fluid solid content described in step (3) is 1 ~ 3%.
Nano-cellulose soliquid described in step (4) and the volume ratio of potassium permanganate solution are 1 ~ 20:1.
The concentration of the potassium permanganate solution described in step (4) is 0.01 ~ 0.1mol/L.
Advantage of the present invention and innovative point are:
Discarded Vegetable Sponge of Luffa is utilized to be raw material, give full play to nano-cellulose good mechanical performance and can be used as the multidirectional effect of natural reducing agent, template and stablizer, when without any additive and finishing, the redox reaction of original position is at room temperature carried out with potassium permanganate, one step prepares good mechanical performance, Heat stability is good and have the nano-manganese dioxide/nano micro crystal cellulose hybrid material of the functions such as optical, electrical magnetic concurrently, and above research has no relevant domestic and foreign literature report.The present invention is not only conducive to the higher value application of Vegetable Sponge of Luffa agriculture and forestry organic waste material, simultaneously also for the simple and easy preparation of functional inorganic phase/nano-cellulose matrix material provides new reference.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction analysis figure of the nano-manganese dioxide powder of gained of the present invention.
Fig. 2 is the Flied emission transmission electron microscope picture (enlargement ratio × 100000) of the nano-manganese dioxide/nano micro crystal cellulose matrix material of gained of the present invention.
Fig. 3 is the Flied emission transmission electron microscope picture (enlargement ratio × 100000) of the nano-manganese dioxide of gained of the present invention.
Embodiment
embodiment 1
(1) discarded Vegetable Sponge of Luffa is cleaned, naturally dry, pulverize, cross 40 mesh sieves, after 105 oven dry 18h to constant weight, be placed in moisture eliminator for subsequent use with sealing bag encapsulation;
(2) luffa vegetable sponge described in step (1) is placed in apparatus,Soxhlet's, with benzene alcoholic solution extracting 6 h at 90 DEG C, with Textone (Glacial acetic acid adjustment) temperature 75 DEG C process 8h in acid condition, use 2% potassium hydroxide, at 90 DEG C, process 4h, with 1% hydrochloric acid reprocessing 2h at 80 DEG C, cooling, be washed till neutrality with deionized water, then obtain Microcrystalline Cellulose powder after carrying out lyophilize, it is for subsequent use that collection is placed in moisture eliminator;
(3) the Microcrystalline Cellulose powder described in step (2) and sulphuric acid soln are pressed 1:10 hybrid reaction 45min, centrifugal, dialysis, concentrated, i.e. obtained nano-cellulose soliquid;
(4) after the nano-cellulose soliquid described in step (3) being mixed ultrasonic 2h with potassium permanganate solution by 1:10, dialysis, until the no change of the color of dialyzate, obtained nano-manganese dioxide/nano micro crystal cellulose composite solution, this solution is placed in culture dish, spontaneous evaporation a couple of days, obtain nano-manganese dioxide/nano micro crystal cellulose laminated film.
embodiment 2
(1) discarded Vegetable Sponge of Luffa is cleaned, naturally dry, pulverize, cross 40 mesh sieves, after 105 oven dry 18h to constant weight, be placed in moisture eliminator for subsequent use with sealing bag encapsulation;
(2) luffa vegetable sponge described in step (1) is placed in apparatus,Soxhlet's, with benzene alcoholic solution extracting 6 h at 90 DEG C, with Textone (Glacial acetic acid adjustment) temperature 75 DEG C process 6h in acid condition, use 2% potassium hydroxide, at 90 DEG C, process 2h, with 1% hydrochloric acid reprocessing 2h at 80 DEG C, cooling, be washed till neutrality with deionized water, then obtain Microcrystalline Cellulose powder after carrying out lyophilize, it is for subsequent use that collection is placed in moisture eliminator;
(3) the Microcrystalline Cellulose powder described in step (2) and sulphuric acid soln are pressed 1:10 hybrid reaction 50min, centrifugal, dialysis, concentrated, i.e. obtained nano-cellulose soliquid;
(4) after the nano-cellulose soliquid described in step (3) being mixed ultrasonic 3h with potassium permanganate solution by 1:5, dialysis, until the no change of the color of dialyzate, obtained nano-manganese dioxide/nano micro crystal cellulose composite solution, this solution is placed in culture dish, spontaneous evaporation a couple of days, obtain nano-manganese dioxide/nano micro crystal cellulose laminated film.
embodiment 3
Adopt ultraviolet-visible pectrophotometer (UV-Vis) to measure nano-manganese dioxide/nano micro crystal cellulose mixture and have absorption peak at 370nm place.
embodiment 4
X-ray diffractometer (XRD) is adopted to measure nano-manganese dioxide powder.
The XRD spectra of nano-manganese dioxide is consistent with the main diffraction peak of Manganse Dioxide standard spectrogram (JCPDS 44-0141).Near 2 θ are positioned at 17.67,25.01,29.81,32.50,38.70,42.28,51.34,53.70,56.86 and 66.31 °, there is obvious diffraction peak, correspond respectively to α-MnO
2(110), (200), (220), (310), (211), (301), (321), (510), (411), (600) crystal face, its degree of crystallinity is 82%.
embodiment 5
Adopt high resolution Flied emission transmission electron microscope observed result to show nano-manganese dioxide of the present invention to compare and be evenly dispersed in nano-cellulose surface, nano-cellulose is mainly in bar-shaped, and nano-manganese dioxide in the form of sheets, and size is 20 ~ 30nm.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (2)
1. prepare a method for nano-manganese dioxide/nano micro crystal cellulose laminated film, it is characterized in that: comprise the following steps:
(1) discarded Vegetable Sponge of Luffa raw material is cleaned, naturally dry, pulverize, cross 40 mesh sieves, after 105 ~ 110 DEG C of oven dry 12 ~ 24h to constant weight, be placed in moisture eliminator for subsequent use with sealing bag encapsulation;
(2) luffa vegetable sponge described in step (1) is placed in apparatus,Soxhlet's, with benzene alcoholic solution extracting 5 ~ 8 h at 80 ~ 100 DEG C, with Textone 65 ~ 85 DEG C of process 6 ~ 9h in acid condition, with massfraction be 1 ~ 6% potassium hydroxide solution at 80 ~ 100 DEG C, process 3 ~ 5h, be hydrochloric acid reprocessing 1 ~ 3h at 70 ~ 90 DEG C of 0.5 ~ 2% with massfraction, cooling, is washed till neutrality with deionized water, obtain Microcrystalline Cellulose powder after carrying out lyophilize again, it is for subsequent use that collection is placed in moisture eliminator;
(3) by the Microcrystalline Cellulose powder described in step (2) and massfraction be the sulphuric acid soln hybrid reaction 30 ~ 60min of 64 %, centrifugal, dialysis, concentrated, i.e. obtained nano-cellulose soliquid;
(4) dialyse after the nano-cellulose soliquid described in step (3) being mixed ultrasonic 1 ~ 6h with potassium permanganate solution, until the no change of the color of dialyzate, obtained nano-manganese dioxide/Nanocrystalline Cellulose Colloid mixture, be placed on again in culture dish, spontaneous evaporation a couple of days, obtain nano-manganese dioxide/nano micro crystal cellulose laminated film;
Acidic conditions described in step (2) is pH=4 ~ 5, adopts Glacial acetic acid to regulate;
Benzene alcoholic solution described in step (2) is benzene-alcohol mixeding liquid, and its volume ratio is 1.5 ~ 2.5:1;
The quality of the Microcrystalline Cellulose powder described in step (3) and the volume ratio of sulfuric acid are 1 g:8 ~ 12mL;
Concentrated rear obtained nano-cellulose colloidal suspension fluid solid content described in step (3) is 1 ~ 3%;
Nano-cellulose soliquid described in step (4) and the volume ratio of potassium permanganate solution are 1 ~ 20:1;
The concentration of the potassium permanganate solution described in step (4) is 0.01 ~ 0.1mol/L.
2. the method preparing nano-manganese dioxide/nano micro crystal cellulose laminated film according to claim 1, is characterized in that: the hybrid reaction temperature described in step (3) is 30 ~ 60 DEG C.
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| CN104017243B (en) * | 2014-05-26 | 2017-01-04 | 北京印刷学院 | A kind of based on native cellulose can be degradable antibacterial fresh-keeping packaging material and preparation method thereof |
| CN105037812A (en) * | 2015-08-21 | 2015-11-11 | 广西大学 | Antimicrobial degradable packaging material and preparation method thereof |
| CN107419619A (en) * | 2015-09-01 | 2017-12-01 | 蒋春花 | The strong sandwich sheet of Resisting fractre ability and preparation method |
| CN105086487A (en) * | 2015-09-01 | 2015-11-25 | 佛山蓝途科技有限公司 | Muffling purification high-temperature resistant material for automobile exhaust pipeline and preparation method of muffling purification high-temperature resistant material |
| CN106000340A (en) * | 2016-06-13 | 2016-10-12 | 石狮市三小福服饰有限公司 | Preparation method of manganese dioxide cellulose nanofiber mixed compound |
| CN106106720A (en) * | 2016-06-27 | 2016-11-16 | 郭迎庆 | A kind of antibacterial degradable loofah fiber membrane preparation method |
| CN106495225B (en) * | 2016-10-26 | 2018-04-13 | 中山大学 | A kind of polysaccharide hydridization manganese dioxide nano particle and its preparation method and purposes for magnetic resonance development |
| CN107739055A (en) * | 2017-11-02 | 2018-02-27 | 太原工业学院 | A kind of method that biological template method prepares nanometer titanium dioxide manganese material |
| CN109289782A (en) * | 2018-10-10 | 2019-02-01 | 太原工业学院 | A kind of manganese dioxide/corn stover nano material and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB1138087A (en) * | 1966-10-13 | 1968-12-27 | Criterion Plates Papers Films | Improvements relating to photographic processes and films |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB1138087A (en) * | 1966-10-13 | 1968-12-27 | Criterion Plates Papers Films | Improvements relating to photographic processes and films |
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