CN103131033A - 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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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 for preparing nano-manganese dioxide/nano micro crystal cellulose laminated film.
Background technology
Mierocrystalline cellulose is the abundantest in the world biodegradable, reproducible natural macromolecular material, and plant is annual by photosynthesis, can produce the Mierocrystalline cellulose of hundreds of millions tons.The crystalline state nano-cellulose is the structural support of natural cellulose matrix material, isolates nano-cellulose from natural cellulose, and consequent nanoscale effect makes it have superior mechanical property.Control nano-cellulose molecule and supramolecular aggregation thereof in the multiple dimensioned scope of micro-nano, further formulate out thus the new nanometer fine chemical product with excellent function, new nano material, become Disciplinary Frontiers and the tackling key problem focus of Cellulose Science research at present.
Although inorganic nano material chemical constitution adjustable, functional performance is flexibly enriched, 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, its higher specific surface area, a large amount of active reaction sites of meticulous tridimensional nano net structure and surface can be used as " biological template agent " and use, to obtain pattern, size is controlled and the nano composite material that is evenly distributed.With nano-inorganic substance, NCC is adulterated, not only can make nano-cellulose obtain more excellent mechanical property, can give the functions such as the more abundant light of NCC, electricity, magnetic, absorption, catalysis simultaneously.Therefore, this novel biomaterial of nano-cellulose and various functional inorganic nanos are carried out mutually compound, the product innovation of generation and new function can't be estimated.To sum up, carry out controlled preparation and the performance study of functional type nano-inorganic substance/nano-cellulose matrix material, have important scientific meaning for promoting the applied research of nano-cellulose in new technology, novel material and new forms of energy.Take potassium permanganate as oxygenant, the nano-cellulose soliquid that utilizes discarded Vegetable Sponge of Luffa to make is stablizer, template and reductive agent, and the correlative study that original position is prepared nano-manganese dioxide/nano micro crystal cellulose laminated film there is not yet report.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing nano-manganese dioxide/nano micro crystal cellulose laminated film, it is a kind ofly to utilize 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 is to utilize the nano-cellulose soliquid to be 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 the matrix material that has the functions such as light, heat, electromagnetism concurrently.
For achieving the above object, the present invention adopts following technical scheme:
A kind of method for preparing nano-manganese dioxide/nano micro crystal cellulose laminated film comprises the following steps:
(1) will discard the Vegetable Sponge of Luffa raw material and clean, and naturally dry, and pulverize, and cross 40 mesh sieves, 105 ~ 110 ℃ of oven dry 12 ~ 24h are placed in moisture eliminator standby with the sealing bag encapsulation to constant weight;
(2) luffa vegetable sponge described in step (1) is placed in apparatus,Soxhlet's, with the benzene alcoholic solution at 80 ~ 100 ℃ of lower extracting 5 ~ 8 h, with Textone 65 ~ 85 ℃ of processing 6 ~ 9h under acidic conditions, be that 1 ~ 6% potassium hydroxide solution is processed 3 ~ 5h with massfraction under 80 ~ 100 ℃, be that 0.5 ~ 2% hydrochloric acid is processed 1 ~ 3h again with massfraction under 70 ~ 90 ℃, cooling, be washed till neutrality with deionized water, carry out getting the Microcrystalline Cellulose powder after lyophilize, it is standby that collection is placed in moisture eliminator again;
(3) the sulphuric acid soln hybrid reaction 30 ~ 60min that the Microcrystalline Cellulose powder described in step (2) and massfraction is 64 %, centrifugal, dialysis, concentrated, namely make the nano-cellulose soliquid;
(4) after being mixed ultrasonic 1 ~ 6h with potassium permanganate solution, the nano-cellulose soliquid described in step (3) dialyses, until the color of dialyzate does not change, make nano-manganese dioxide/Nanocrystalline Cellulose Colloid mixture, be placed on again in culture dish, spontaneous evaporation a couple of days, namely get nano-manganese dioxide/nano micro crystal cellulose laminated film.
The described benzene alcoholic solution of step (2) is benzene-alcohol mixeding liquid, and its volume ratio is 1.5 ~ 2.5:1.
The described acidic conditions of step (2) is pH=4 ~ 5, adopts Glacial acetic acid to regulate.
The quality of the described Microcrystalline Cellulose powder of step (3) and the volume ratio of sulfuric acid are 1 g:8 ~ 12mL.
The described hybrid reaction temperature of step (3) is 30 ~ 60 ℃.
Step (3) is described, and to make nano-cellulose colloidal suspension fluid solid content after concentrated be 1 ~ 3%.
The volume ratio of the described nano-cellulose soliquid of step (4) and potassium permanganate solution is 1 ~ 20:1.
The concentration of the described potassium permanganate solution of step (4) is 0.01 ~ 0.1mol/L.
Advantage of the present invention and innovative point are:
Utilize discarded Vegetable Sponge of Luffa to be raw material, the multidirectional effect of giving full play to the nano-cellulose good mechanical performance and can be used as natural reducing agent, template and stablizer, in the situation that without any additive and finishing, at room temperature carry out the redox reaction of original position with potassium permanganate, one step prepared good mechanical performance, Heat stability is good and had the nano-manganese dioxide of the functions such as light, electromagnetism/nano micro crystal cellulose hybrid material concurrently, and above research has no relevant domestic and foreign literature report.The present invention not only is conducive to the higher value application of Vegetable Sponge of Luffa agriculture and forestry organic waste material, and the while also provides new reference for the simple and easy preparation of functional inorganic phase/nano-cellulose matrix material.
Description of drawings
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 field transmission Electronic Speculum figure (enlargement ratio * 100000) of the nano-manganese dioxide/nano micro crystal cellulose matrix material of gained of the present invention.
Fig. 3 is the field transmission Electronic Speculum figure (enlargement ratio * 100000) of the nano-manganese dioxide of gained of the present invention.
Embodiment
Embodiment 1
(1) will discard Vegetable Sponge of Luffa and clean, and naturally dry, and pulverize, and cross 40 mesh sieves, 105 oven dry 18h are placed in moisture eliminator standby with the sealing bag encapsulation to constant weight;
(2) luffa vegetable sponge described in step (1) is placed in apparatus,Soxhlet's, with the benzene alcoholic solution at 90 ℃ of lower extracting 6 h, 75 ℃ of (Glacial acetic acid adjusting) temperature are processed 8h under acidic conditions with Textone, use 2% potassium hydroxide, process 4h under 90 ℃, process again 2h with 1% hydrochloric acid under 80 ℃, cooling, be washed till neutrality with deionized water, then carry out getting the Microcrystalline Cellulose powder after lyophilize, it is standby 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, namely make the nano-cellulose soliquid;
(4) the nano-cellulose soliquid described in step (3) is mixed ultrasonic 2h with potassium permanganate solution by 1:10 after, dialysis, until the color of dialyzate does not change, make nano-manganese dioxide/nano micro crystal cellulose composite solution, this solution is placed in culture dish, spontaneous evaporation a couple of days, namely get nano-manganese dioxide/nano micro crystal cellulose laminated film.
Embodiment 2
(1) will discard Vegetable Sponge of Luffa and clean, and naturally dry, and pulverize, and cross 40 mesh sieves, 105 oven dry 18h are placed in moisture eliminator standby with the sealing bag encapsulation to constant weight;
(2) luffa vegetable sponge described in step (1) is placed in apparatus,Soxhlet's, with the benzene alcoholic solution at 90 ℃ of lower extracting 6 h, 75 ℃ of (Glacial acetic acid adjusting) temperature are processed 6h under acidic conditions with Textone, use 2% potassium hydroxide, process 2h under 90 ℃, process again 2h with 1% hydrochloric acid under 80 ℃, cooling, be washed till neutrality with deionized water, then carry out getting the Microcrystalline Cellulose powder after lyophilize, it is standby 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, namely make the nano-cellulose soliquid;
(4) the nano-cellulose soliquid described in step (3) is mixed ultrasonic 3h with potassium permanganate solution by 1:5 after, dialysis, until the color of dialyzate does not change, make nano-manganese dioxide/nano micro crystal cellulose composite solution, this solution is placed in culture dish, spontaneous evaporation a couple of days, namely get 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 at the 370nm place, absorption peak is arranged.
Embodiment 4
Adopt X-ray diffractometer (XRD) to measure the nano-manganese dioxide powder.
The XRD spectra of nano-manganese dioxide consistent with the main diffraction peak of Manganse Dioxide standard spectrogram (JCPDS 44-0141).Obvious diffraction peak occurs 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 °, 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 field transmission electron microscopy observation result to show that nano-manganese dioxide of the present invention relatively is evenly dispersed in the nano-cellulose surface, it is bar-shaped that nano-cellulose mainly is, and nano-manganese dioxide in the form of sheets, and size is 20 ~ 30nm.
The above is only preferred embodiment of the present invention, and all equalizations of doing 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 (8)
1. method for preparing nano-manganese dioxide/nano micro crystal cellulose laminated film is characterized in that: comprise the following steps:
(1) will discard the Vegetable Sponge of Luffa raw material and clean, and naturally dry, and pulverize, and cross 40 mesh sieves, 105 ~ 110 ℃ of oven dry 12 ~ 24h are placed in moisture eliminator standby with the sealing bag encapsulation to constant weight;
(2) luffa vegetable sponge described in step (1) is placed in apparatus,Soxhlet's, with the benzene alcoholic solution at 80 ~ 100 ℃ of lower extracting 5 ~ 8 h, with Textone 65 ~ 85 ℃ of processing 6 ~ 9h under acidic conditions, be that 1 ~ 6% potassium hydroxide solution is processed 3 ~ 5h with massfraction under 80 ~ 100 ℃, be that 0.5 ~ 2% hydrochloric acid is processed 1 ~ 3h again with massfraction under 70 ~ 90 ℃, cooling, be washed till neutrality with deionized water, carry out getting the Microcrystalline Cellulose powder after lyophilize, it is standby that collection is placed in moisture eliminator again;
(3) the sulphuric acid soln hybrid reaction 30 ~ 60min that the Microcrystalline Cellulose powder described in step (2) and massfraction is 64 %, centrifugal, dialysis, concentrated, namely make the nano-cellulose soliquid;
(4) after being mixed ultrasonic 1 ~ 6h with potassium permanganate solution, the nano-cellulose soliquid described in step (3) dialyses, until the color of dialyzate does not change, make nano-manganese dioxide/Nanocrystalline Cellulose Colloid mixture, be placed on again in culture dish, spontaneous evaporation a couple of days, namely get nano-manganese dioxide/nano micro crystal cellulose laminated film.
2. the method for preparing nano-manganese dioxide/nano micro crystal cellulose laminated film according to claim 1, it is characterized in that: the described benzene alcoholic solution of step (2) is benzene-alcohol mixeding liquid, and its volume ratio is 1.5 ~ 2.5:1.
3. the method for preparing nano-manganese dioxide/nano micro crystal cellulose laminated film according to claim 1, it is characterized in that: the described acidic conditions of step (2) is pH=4 ~ 5, adopts Glacial acetic acid to regulate.
4. the method for preparing nano-manganese dioxide/nano micro crystal cellulose laminated film according to claim 1, it is characterized in that: the quality of the described Microcrystalline Cellulose powder of step (3) and the volume ratio of sulfuric acid are 1 g:8 ~ 12mL.
5. the method for preparing nano-manganese dioxide/nano micro crystal cellulose laminated film according to claim 1, it is characterized in that: the described hybrid reaction temperature of step (3) is 30 ~ 60 ℃.
6. the method for preparing nano-manganese dioxide/nano micro crystal cellulose laminated film according to claim 1 is characterized in that: step (3) is described, and to make nano-cellulose colloidal suspension fluid solid content after concentrated be 1 ~ 3%.
7. the method for preparing nano-manganese dioxide/nano micro crystal cellulose laminated film according to claim 1, it is characterized in that: the volume ratio of the described nano-cellulose soliquid of step (4) and potassium permanganate solution is 1 ~ 20:1.
8. the method for preparing nano-manganese dioxide/nano micro crystal cellulose laminated film according to claim 1, it is characterized in that: the concentration of the described potassium permanganate solution of step (4) is 0.01 ~ 0.1mol/L.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017243A (en) * | 2014-05-26 | 2014-09-03 | 北京印刷学院 | Completely degradable antibacterial fresh-keeping packaging material based on natural cellulose and preparation method thereof |
| CN105037812A (en) * | 2015-08-21 | 2015-11-11 | 广西大学 | Antimicrobial degradable packaging material and preparation method thereof |
| 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 |
| CN106495225A (en) * | 2016-10-26 | 2017-03-15 | 中山大学 | A kind of polysaccharide hydridization manganese dioxide nano particle and its preparation method and purposes for magnetic resonance development |
| CN107419619A (en) * | 2015-09-01 | 2017-12-01 | 蒋春花 | The strong sandwich sheet of Resisting fractre ability and preparation method |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1138087A (en) * | 1966-10-13 | 1968-12-27 | Criterion Plates Papers Films | Improvements relating to photographic processes and films |
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2013
- 2013-03-20 CN CN201310089398.6A patent/CN103131033B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1138087A (en) * | 1966-10-13 | 1968-12-27 | Criterion Plates Papers Films | Improvements relating to photographic processes and films |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017243A (en) * | 2014-05-26 | 2014-09-03 | 北京印刷学院 | Completely degradable antibacterial fresh-keeping packaging material based on natural cellulose and preparation method thereof |
| CN105037812A (en) * | 2015-08-21 | 2015-11-11 | 广西大学 | Antimicrobial degradable packaging material and preparation method thereof |
| 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 |
| CN107419619A (en) * | 2015-09-01 | 2017-12-01 | 蒋春花 | The strong sandwich sheet of Resisting fractre ability and preparation method |
| 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 |
| CN106495225A (en) * | 2016-10-26 | 2017-03-15 | 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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