CN106146899A - A kind of stannic oxide/graphene nano microcrystalline cellulose composite material thin film and preparation method thereof - Google Patents
A kind of stannic oxide/graphene nano microcrystalline cellulose composite material thin film and preparation method thereof Download PDFInfo
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- CN106146899A CN106146899A CN201610464253.3A CN201610464253A CN106146899A CN 106146899 A CN106146899 A CN 106146899A CN 201610464253 A CN201610464253 A CN 201610464253A CN 106146899 A CN106146899 A CN 106146899A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/04—Oxycellulose; Hydrocellulose
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Abstract
The invention belongs to composite material film field, disclose a kind of stannic oxide/graphene nano microcrystalline cellulose composite material thin film and preparation method thereof.Described preparation method comprises the following steps: graphite powder oxidation is peeled off by (1), is subsequently adding paper pulp and is hydrolyzed rapidly, then terminates reaction, washing, and filtration to filter cake pH is neutrality；(2), during filter cake is redispersed in water, dialysis, ultrafiltration obtains stannic oxide/graphene nano microcrystalline cellulose composite material thin film.Preparation method of the present invention safety simple to operate, technological process is short, product good physical performance, provides the new method of simple and fast for the preparation of high physical property composite material film.The stannic oxide/graphene nano microcrystalline cellulose composite material thin film that the present invention prepares has the advantages such as nano micro crystal cellulose component orientation rule, marshalling, thin film hot strength and elastic modelling quantity are big, is with a wide range of applications in field of compound material.
Description
Technical field
The invention belongs to composite material film field, be specifically related to a kind of graphene oxide-nano micro crystal cellulose and be combined
Material film and preparation method thereof.
Background technology
Graphene oxide is the topmost derivant of " mother of material with carbon element "-Graphene, similar with Graphene except having
Two-dimensional structure, outside the feature of nano-scale and stable performance, its edge there is also abundant oxygen-containing functional group, give it
Excellent dissolubility, physical property and reactivity.Meanwhile, because the reason of structure, graphene oxide be also have most uncommon
Hope the graphene-based material realizing large-scale production.
Nano micro crystal cellulose is the cellulosic material of a kind of nano-scale, also referred to as " cellulose nano microcrystalline ".It
Diameter be generally 5～20nm, length is generally 10nm～1 μm, and draw ratio scope is 1～100.Nano micro crystal cellulose has
Raw material sources is extensive, and the feature such as easily biological-degradable and good physical properties can apply to the various aspects of Material Field.
Report currently, with respect to graphene oxide and the composite material film of nano micro crystal cellulose composition is the most many.
The features such as it is low that this type of conventional composite material film has density, flexible and good biocompatibility.But, existing preparation technology
Generally require and prepare graphene oxide and nano micro crystal cellulose respectively, then carry out both compound these three steps, there is production
The defects such as the cycle is long, and cost height is low with yield.Therefore, find one and rapidly and efficiently prepare graphene oxide-nano microcrystalline fiber
The method of element composite material film is highly desirable to.
Summary of the invention
In place of shortcoming and defect for solution prior art, the primary and foremost purpose of the present invention is to provide a kind of graphite oxide
The preparation method of alkene-nano micro crystal cellulose composite material film.This preparation method is prepared quickly and easily by one kettle way
Stability Analysis of Structures, the graphene oxide-nano micro crystal cellulose composite material film of function admirable.
Another object of the present invention is to provide a kind of composite material film obtained by above-mentioned preparation method.
The object of the invention is achieved through the following technical solutions:
A kind of one kettle way prepares the method for graphene oxide-nano micro crystal cellulose composite material film, including following step
Rapid:
(1) 2～4 mass parts graphite powders are added in 200～400 parts by volume mixed acid, be then slowly added into 12～24 matter
Amount part KMnO4And stir；It is warming up to 45～55 DEG C and is incubated 9～15h, obtaining atropurpureus suspension；Gained suspension falls
Enter in 200～400 mass parts mixture of ice and water cool down, add 20～40 mass parts (over dry weight) paper pulp and stir reaction 10～
20min, continuously adds 2～4 parts by volume H2O2Solution, obtains bright yellow solution；Filtering, solid is repeatedly with hot wash, filtration extremely
PH is neutrality；
(2) filter cake of step (1) gained is dispersed again in water, dialyse one week to remove salt and saccharide impurity, super
Filter and i.e. obtain graphene oxide-nano micro crystal cellulose composite material film.
Step (1) described mixed acid be volume ratio be concentrated sulphuric acid and the mixing of strong phosphoric acid of 9:1；The quality of described sulphuric acid is dense
Degree is 98%；The mass concentration of strong phosphoric acid is preferably 85%.
The speed of step (1) described stirring is both preferably 300～400r/min.
Step (1) course of reaction is the most preferably carried out in the oil bath pan of band magnetic agitation.
In step (1), suspension is poured into and is cooled down 4～8min in mixture of ice and water.
Step (1) described hot water is preferably the hot distilled water of 60 DEG C.
Step (1) described H2O2The mass concentration of solution is preferably 30%.
Step (2) described dialysis preferably employs the PVCF film of 10000 molecular cut offs and dialyses, dialysis medium for go from
Sub-water.
Step (2) described ultrafiltration, the ultrafilter membrane aperture of use is 0.22 μm, and pressure is 0.24MPa.
A kind of graphene oxide-nano micro crystal cellulose composite material film prepared by above-mentioned preparation method.Should
Nano micro crystal cellulose in composite material film has a neat arrangement, wherein nanofiber fiber element a diameter of 30～
40nm, a length of 200～300nm, and stannic oxide/graphene nano layer are combined with each other closely so that drawing of composite material film
Stretching intensity and reach 100～300MPa, elastic modelling quantity reaches 10～20GPa.
The present invention is prepared for graphene oxide-nano micro crystal cellulose composite material film the most quickly and easily,
There is the advantages such as nano micro crystal cellulose component orientation rule, marshalling, thin film hot strength and elastic modelling quantity are big, compound
Material Field is with a wide range of applications.
Compared with prior art, the present invention has the following advantages and beneficial effect:
One kettle way technique not only simplify the preparation flow of composite material film, reduces production cost, decreases environment
Pollute, it is ensured that the physical property of product.The method is that the high physical property manufacturing and can being applied to field of compound material is thin
Membrane material provides Technical Reference.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
Graphite powder 2g is put into mix homogeneously in 200mL mixed acid (concentrated sulphuric acid: strong phosphoric acid=9:1 (v:v)), then delays
Slow addition 12g KMnO4With the speed uniform stirring of 300r/min in ice-water bath, it is warming up to 45 DEG C and is incubated 9h；Gained purple is black
Color suspension pours cooling 4min in 200g mixture of ice and water into, adds 20g (over dry weight) paper pulp and stirs with the speed of 300r/min
Mix reaction 10min, continuously add the H of 2mL 30%2O2Solution, obtains bright yellow solution；Filtering, filter cake is repeatedly by the warm of 60 DEG C
Distilled water wash, filtration to pH are neutrality；
The filter cake of gained is dispersed again in water, dialyse one week to remove salt and saccharide impurity, ultrafiltration i.e. obtains oxidation stone
Ink alkene-nano micro crystal cellulose composite material film.Nano micro crystal cellulose in this composite material film has neat row
Row so that the hot strength of composite material film reaches 100MPa, and elastic modelling quantity reaches 10GPa.
Embodiment 2
Graphite powder 3g is put into mix homogeneously in 300mL mixed acid (concentrated sulphuric acid: strong phosphoric acid=9:1 (v:v)), then delays
Slow addition 18g KMnO4With the speed uniform stirring of 350r/min in ice-water bath, it is warming up to 50 DEG C and is incubated 12h；Gained is purple
Black suspension pours cooling 6min in 300g mixture of ice and water into, adds 30g (over dry weight) paper pulp the speed with 350r/min
Stirring reaction 15min, continuously adds the H of 3mL 30%2O2Solution, obtains bright yellow solution；Filtering, filter cake is repeatedly with 60 DEG C
Hot distilled water washing, filtration to pH are neutrality；
The filter cake of gained is dispersed again in water, dialyse one week to remove salt and saccharide impurity, ultrafiltration i.e. obtains oxidation stone
Ink alkene-nano micro crystal cellulose composite material film.Nano micro crystal cellulose in this composite material film has neat row
Row so that the hot strength of composite material film reaches 200MPa, and elastic modelling quantity reaches 15GPa.
Embodiment 3
Graphite powder 4g is put into mix homogeneously in 400mL mixed acid (concentrated sulphuric acid: strong phosphoric acid=9:1 (v:v)), then delays
Slow addition 24g KMnO4With the speed uniform stirring of 400r/min in ice-water bath, it is warming up to 55 DEG C and is incubated 15h；Gained is purple
Black suspension pours cooling 8min in 400g mixture of ice and water into, adds 40g (over dry weight) paper pulp the speed with 400r/min
Stirring reaction 20min, continuously adds the H of 4mL 30%2O2Solution, obtains bright yellow solution；Filtering, filter cake is repeatedly with 60 DEG C
Hot distilled water washing, filtration to pH are neutrality；
The filter cake of gained is dispersed again in water, dialyse one week to remove salt and saccharide impurity, ultrafiltration i.e. obtains oxidation stone
Ink alkene-nano micro crystal cellulose composite material film.Nano micro crystal cellulose in this composite material film has neat row
Row so that the hot strength of composite material film reaches 300MPa, and elastic modelling quantity reaches 20GPa.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limit, the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify,
All should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (9)
1. the preparation method of graphene oxide-nano micro crystal cellulose composite material film, it is characterised in that include following
Step:
(1) 2～4 mass parts graphite powders are added in 200～400 parts by volume mixed acid, be subsequently adding 12～24 mass parts KMnO4
And stir；Being warming up to 45～55 DEG C and be incubated 9～15h, gained suspension pours 200～400 mass parts mixture of ice and water into
Middle cooling, addition over dry is heavily the paper pulp of 20～40 mass parts and stirs reaction 10～20min, continuously adds 2～4 parts by volume
H2O2Solution, filters, and solid uses hot wash, filtration to pH to be neutrality repeatedly；
(2) being dispersed again in water by the filter cake of step (1) gained, dialyse one week, ultrafiltration i.e. obtains graphene oxide-nano microcrystalline
Cellulose composite material thin film.
The preparation method of graphene oxide the most according to claim 1-nano micro crystal cellulose composite material film, it is special
Levy and be, step (1) described mixed acid be volume ratio be concentrated sulphuric acid and the mixed acid of strong phosphoric acid of 9:1；The quality of described sulphuric acid
Concentration is 98%.
The preparation method of graphene oxide the most according to claim 1-nano micro crystal cellulose composite material film, it is special
Levying and be, the speed of step (1) described stirring is 300～400r/min.
The preparation method of graphene oxide the most according to claim 1-nano micro crystal cellulose composite material film, it is special
Levying and be, in step (1), suspension is poured into and is cooled down 4～8min in mixture of ice and water.
The preparation method of graphene oxide the most according to claim 1-nano micro crystal cellulose composite material film, it is special
Levying and be, step (1) described hot water is the hot distilled water of 60 DEG C.
The preparation method of graphene oxide the most according to claim 1-nano micro crystal cellulose composite material film, it is special
Levy and be, step (1) described H2O2The concentration of solution is 30%.
The preparation method of graphene oxide the most according to claim 1-nano micro crystal cellulose composite material film, it is special
Levying and be, step (2) described dialysis is that the PVCF film using 10000 molecular cut offs is dialysed, and dialysis medium is deionization
Water.
The preparation method of graphene oxide the most according to claim 1-nano micro crystal cellulose composite material film, it is special
Levying and be, step (2) described ultrafiltration, the ultrafilter membrane aperture of use is 0.22 μm, and pressure is 0.24MPa.
9. graphene oxide-nano micro crystal cellulose composite material film, it is characterised in that it is by claim 1 to 8 times
The preparation method of one described graphene oxide-nano micro crystal cellulose composite material film prepares.
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Cited By (6)
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| CN107789667A (en) * | 2017-10-12 | 2018-03-13 | 广州贝奥吉因生物科技有限公司 | A kind of porous compound support frame for promoting regenerating bone or cartilage and preparation method thereof |
| CN109195236A (en) * | 2018-11-05 | 2019-01-11 | 厦门信果石墨烯科技有限公司 | A kind of graphene fever power generating glass and its manufacturing method |
| CN110358150A (en) * | 2019-06-10 | 2019-10-22 | 浙江金昌特种纸股份有限公司 | A kind of nano-cellulose/graphene is compound to prepare flexible electron display screen method |
| CN110651335A (en) * | 2017-03-17 | 2020-01-03 | 夸祖鲁-纳塔尔大学 | Conductive composite material |
| CN114805942A (en) * | 2022-05-19 | 2022-07-29 | 浙江理工大学 | Preparation method of RGO/CNC/CNF composite film |
| US11845853B2 (en) | 2022-05-19 | 2023-12-19 | Zhejiang Sci-Tech University | Preparation method of composite films based on cellulose nanocrystals, cellulose nanofibers and reduced graphene oxide |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110651335A (en) * | 2017-03-17 | 2020-01-03 | 夸祖鲁-纳塔尔大学 | Conductive composite material |
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| CN107789667A (en) * | 2017-10-12 | 2018-03-13 | 广州贝奥吉因生物科技有限公司 | A kind of porous compound support frame for promoting regenerating bone or cartilage and preparation method thereof |
| CN107789667B (en) * | 2017-10-12 | 2020-12-04 | 广州贝奥吉因生物科技有限公司 | Porous composite scaffold for promoting cartilage regeneration and preparation method thereof |
| CN109195236A (en) * | 2018-11-05 | 2019-01-11 | 厦门信果石墨烯科技有限公司 | A kind of graphene fever power generating glass and its manufacturing method |
| CN110358150A (en) * | 2019-06-10 | 2019-10-22 | 浙江金昌特种纸股份有限公司 | A kind of nano-cellulose/graphene is compound to prepare flexible electron display screen method |
| CN114805942A (en) * | 2022-05-19 | 2022-07-29 | 浙江理工大学 | Preparation method of RGO/CNC/CNF composite film |
| CN114805942B (en) * | 2022-05-19 | 2022-12-16 | 浙江理工大学 | Preparation method of RGO/CNC/CNF composite film |
| US11845853B2 (en) | 2022-05-19 | 2023-12-19 | Zhejiang Sci-Tech University | Preparation method of composite films based on cellulose nanocrystals, cellulose nanofibers and reduced graphene oxide |
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