CN105694074B - A kind of preparation method of the high dielectric nano composite membrane of flexibility fire-resistant - Google Patents
A kind of preparation method of the high dielectric nano composite membrane of flexibility fire-resistant Download PDFInfo
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Abstract
The invention discloses high dielectric nano composite membranes of a kind of flexible fire-resistant and preparation method thereof, in order to provide a kind of preparation method of the high dielectric nano composite membrane of fire-resistant simple for process, at low cost, with very high industrialized production ability and environment friendly.The present invention first takes nano-cellulose to be dispersed in water to form nano-cellulose suspension, and suitable montmorillonite suspension liquid and redox graphene wet feed is added, and quickly filtered filter membrane is drying to obtain product by ultrasonic disperse after stirring, negative pressure leaching at room temperature.The method of the present invention is simple for process, in a manner of filtering and form a film, changes traditional casting film-forming, assigns nano composite membrane special layer structure in film forming procedure, and then can assign the superior mechanics of composite membrane and electric property；Method is environmental-friendly, has very high industrialization production ability, can effectively reduce the production cost of composite membrane, basic place mat is made that the application of the high dielectric nano composite membrane of nanometer flexibility fire-resistant.
Description
Technical field
Prepared by present invention design a kind of having the excellent flexibility function membrane material of flame-retarding characteristic, dielectric properties, and in particular to
A kind of preparation method of the high dielectric nano composite membrane of flexibility fire-resistant.
Background technology
Dielectric material is before the electronic enterprises such as high energy storage device, capacitor have prodigious application market and application
Scape, ceramic material are widely used in dielectric material field because it has the characteristics that high dielectric property, low conductivity, low cost.But
Meanwhile ceramic material poor processability, breakdown strength be low and disadvantage that flexibility is poor then hinder significantly it application and
Development.Therefore, the high molecular material such as Kynoar, polyimides, epoxy resin etc. of these disadvantages of ceramic material can be improved,
Become the research hotspot in the field.But current high molecular material has the following problems applied to dielectric material field：Macromolecule
The dielectric constant of material is usually very low, it is difficult to meet requirement；In use, the inflammability of high molecular material also can be big
The big application for hindering polymer dielectric material in some special dimensions such as aerospace；It is petrochemical material limited source, non-renewable,
Environment can be generated and greatly be threatened, so needing to find its substitute.
Cellulosic-based material is since its source is wide, high mechanical strength, the easily performances such as decomposition, environmental-friendly become petrochemical industry material
Expect excellent substitute.And wherein nano-cellulose fiber (CNFs) has high draw ratio, higher elasticity modulus, relatively low
Density, higher crystallinity and (Isogai, A., T.Saito, and the features such as smaller coefficient of thermal expansion
H.Fukuzumi,TEMPO-oxidized cellulose nanofibers.Nanoscale,2011.3(1):p.71-85)。
It can be endowed different excellent properties with the difference of additive by the nanocomposite of matrix of nano-cellulose.Stone
Black alkene is a kind of graphite material of single layer, has extremely excellent mechanical performance, the conductivity of superelevation, great specific surface area etc.
Property, great researching value.This seminar (Gao, K., et al., Cellulose in the research of early period
nanofibers/reduced graphene oxide flexible transparent conductive
paper.Carbohydrate Polymers,2013.97(1):P.243-251 it) can be promoted and be received using layer-by-layer
The electrical property of rice cellophane.But by the electrical property of the film of addition graphene modified cellulose base, there are many to ask at present
Topic, if dispersibility is poor in cellulosic matrix for graphene nano lamella, strong influence composite material electrical property and machine
Tool performance, while dispersion process complicated and time consumption, this also greatly limits the production application of cellophane.
Invention content
It is high the purpose of the invention is to provide a kind of fire-resistant with higher anti-flammability, dielectric constant, mechanical performance
The preparation method of dielectric nano composite membrane, this method is simple for process, and cost is relatively low, have very high industrialized production ability and
Environment friendly.
The present invention is achieved by the following technical solution：
A kind of preparation method of the high dielectric nano composite membrane of flexibility fire-resistant, including step：
A. nano-cellulose is taken to be dispersed in water to form nano-cellulose suspension in a reservoir, according to montmorillonite and reduction
Suitable montmorillonite suspension liquid and redox graphene wet feed is added, at room temperature quickly in the mass fraction of graphene oxide
Stirring at least 30 minutes；
B. the mixed liquor stirred evenly is subjected to ultrasonic disperse, forms the mixed dispersion liquid dispersed evenly and stably；
C. dispersion liquid is placed in and is filtered in cup, filter membrane used is the microfiltration membranes that aperture is 0.2 μm, negative pressure leaching；
D. filtered filter membrane is placed in not higher than 70 DEG C temperature dryings, obtains uniform nano composite membrane, as product；
Montmorillonite is a kind of electronegative silicate lamella in surface by nano thickness, the heap by the electrostatic interaction of interlayer
The earthy mineral constituted together are accumulated, the structure cell in crystal structure is by pressing from both sides one layer of alumina octahedral among two layers of oxygen-octahedron
Body is constituted.As common fire retardant, montmorillonite is usually applied to high molecular flame-retardant modified.
The mass percent of montmorillonite, redox graphene and nano-cellulose fiber in above-mentioned preparation method matches
For：Montmorillonite 10%~50%, redox graphene 10%~20%, remainder are nano-cellulose fiber.
Further, the solid content of nano-cellulose suspension is 0.027% in the step a, and solvent is deionized water.
It is further preferred that the carbon-to-oxygen ratio of the redox graphene is 8:1.
Further, the montmorillonite is sodium-based montmorillonite.
It is further preferred that a diameter of 6~8nm of the nano-cellulose, length is 1~2 μm.
Further, the thickness of filtered filter membrane is 20 μm~30 μm in the step d.The filter membrane of the thickness is to be dried
Mechanical property and electric property afterwards is best.
Further, the nano-cellulose aoxidizes wood pulp cellulose for TEMPO and is made by Ultrasonic Pulverization effect stripping
.
Further, the preparation method of the high dielectric nano composite membrane of the flexible fire-resistant, it is characterised in that：The step
Drying process not air blast in rapid d.
The present invention has the advantages that：
1, the method and process of the present invention preparation high dielectric nano composite membrane of nanometer flexibility fire-resistant is simple, to filter the side of film forming
Formula changes traditional casting film-forming, assigns nano composite membrane special layer structure in film forming procedure, and then can assign
The superior mechanics of composite membrane and electric property.
2, the method for the high dielectric nano composite membrane of nanometer flexibility fire-resistant prepared by the present invention is environmental-friendly, has very high
Industrialization production ability can effectively reduce the production cost of composite membrane, to the high dielectric nano composite membrane of nanometer flexibility fire-resistant
Using being made that basic place mat.
Description of the drawings
Fig. 1 is the pictorial diagram of the high dielectric nano composite membrane of nanometer flexibility fire-resistant prepared by the formula of embodiment 1；
Fig. 2 is the pictorial diagram of the high dielectric nano composite membrane of nanometer flexibility fire-resistant prepared by the formula of embodiment 3；
Fig. 3 is the bending fold figure of the high dielectric nano composite membrane of nanometer flexibility fire-resistant prepared by the formula of embodiment 3.
Specific implementation mode
With reference to specific embodiment, the present invention will be further described.The embodiment is only the preferred implementation of the present invention
Example, is not intended to restrict the invention, for those skilled in the art, the present invention can have various changes and change
Change.All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in the present invention
Protection domain within.
Embodiment 1
Listed by table 1 is the preparation formulation Example of the high dielectric nano composite membrane of flexible fire-resistant, and table 2 is that corresponding table 1 is flexible
The performance indicator of the high dielectric nano composite membrane of fire-resistant.Fig. 1,2,3 are the photographs of the high dielectric nano composite membrane of the flexible fire-resistant of corresponding table 1
Piece.
The preparation method of the listed high dielectric nano composite membrane of nanometer flexibility fire-resistant is in table 1：
1, nano-cellulose suspension is taken, is separately added into right amount according to the mass fraction of montmorillonite and redox graphene
Montmorillonite suspension liquid and redox graphene wet feed, be stirred at room temperature 30 minutes.
2, the nano-cellulose stirred evenly, montmorillonite, redox graphene suspension are placed in supersonic cleaning machine
Ultrasound, until whole system is uniformly dispersed.
3, evenly dispersed suspension is placed in and is filtered in cup, the use of aperture is that 0.2 μm of polytetrafluoroethylene (PTFE) microfiltration membranes filters
Until forming uniform film on polytetrafluoroethylene film.
4, filter paper is placed in 70 DEG C of drying in baking oven, obtains nano composite membrane.
The preparation formulation Example of 1 nanometer of high dielectric nano composite membrane of flexible fire-resistant of table
The performance indicator of the high dielectric nano composite membrane of the flexible fire-resistant of table 2
In embodiment 2, after montmorillonite is added, relative to pure nano-cellulose film, thermal stability, anti-flammability and dielectric
Performance is greatly improved.At the same time, when redox graphene is added, dielectric properties are multiplied, and heat
Performance and anti-flammability also improve.The hot property of the high dielectric nano composite membrane of flexible fire-resistant of last gained, anti-flammability,
Dielectric properties are splendid, have and apply productive value well.
Hot property in embodiment is measured, temperature by thermogravimetric heat differential synthesis thermal analyzer (6200 LAB SYS of TG-DTA)
It it is 50 DEG C to 75 DEG C, heating rate is 10 DEG C/min；Maximum heat release rate and total Heat liberation unit are by miniature calorimeter (FAA-
PCFC it) measures；Dielectric properties are measured at room temperature by impedance analyzer (Agilent 4294A), frequency be 102Hz extremely
107Hz。
Fig. 1,2,3 are the photos in kind of the high dielectric nano composite membrane of the flexible fire-resistant of corresponding table 1.It can be with from Fig. 1 and Fig. 2 comparisons
Find out, great variety has occurred in the film pattern prepared after being added to montmorillonite and graphene, while also can intuitively find out graphite
Olefinic constituent is dispersed in film, phenomena such as reunion.From figure 3, it can be seen that the bending fold of prepared film
Can be that flexibility is very good.
It can be seen that flexible flame retardant, the dielectric nano prepared by the present invention from the performance indicator of each embodiment in table 2
Composite membrane have fabulous toughness, anti-flammability and dielectricity, can micromation, intelligence, functionalization communicator
Application is obtained in material, aviation and photoelectric device, there is prodigious realistic development meaning.
Claims (7)
1. a kind of preparation method of the high dielectric nano composite membrane of flexibility fire-resistant, it is characterised in that：Including step：
A. nano-cellulose is taken to be dispersed in water to form nano-cellulose suspension in a reservoir, according to montmorillonite and reduction-oxidation
Suitable montmorillonite suspension liquid and redox graphene wet feed is added in the mass fraction of graphene, at room temperature quickly stirring
At least 30 minutes；
B. the mixed liquor stirred evenly is subjected to ultrasonic disperse, forms the mixed dispersion liquid dispersed evenly and stably；
C. dispersion liquid is placed in and is filtered in cup, filter membrane used is the microfiltration membranes that aperture is 0.2 μm, negative pressure leaching；
D. filtered filter membrane is placed in not higher than 70 DEG C temperature dryings, obtains uniform nano composite membrane, as product；
The mass percent of montmorillonite, redox graphene and nano-cellulose fiber in above-mentioned preparation method matches：
Montmorillonite 10%~50%,
Redox graphene 10%~20%,
Remainder is nano-cellulose fiber；
The montmorillonite is sodium-based montmorillonite.
2. the preparation method of the high dielectric nano composite membrane of flexibility fire-resistant according to claim 1, it is characterised in that：The step
The solid content of nano-cellulose suspension is 0.027% in rapid a, and solvent is deionized water.
3. the preparation method of the high dielectric nano composite membrane of flexibility fire-resistant according to claim 1, it is characterised in that：It is described to go back
The carbon-to-oxygen ratio of former graphene oxide is 8:1.
4. the preparation method of the high dielectric nano composite membrane of flexibility fire-resistant according to claim 1, it is characterised in that：It is described to receive
A diameter of 6~8nm of rice cellulose, length are 1~2 μm.
5. the preparation method of the high dielectric nano composite membrane of flexibility fire-resistant as claimed in any of claims 1 to 4, special
Sign is：The thickness of filtered filter membrane is 20 μm~30 μm in the step d.
6. the preparation method of the high dielectric nano composite membrane of flexibility fire-resistant according to claim 5, it is characterised in that：It is described to receive
Rice cellulose aoxidizes wood pulp cellulose for TEMPO and is made by Ultrasonic Pulverization effect stripping.
7. the preparation method of the high dielectric nano composite membrane of flexibility fire-resistant according to claim 6, it is characterised in that：The step
Drying process not air blast in rapid d.
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| JP2018011021A (en) * | 2016-07-15 | 2018-01-18 | エコホールディングス株式会社 | Ultra-lightweight solar cell module having antiflaming performance available as interior material or exterior material of building, and building installing the same and disaster prevention solar cell module using the same |
| CN107022895B (en) * | 2017-03-17 | 2020-03-27 | 南通纺织丝绸产业技术研究院 | Fabric with flame-retardant coating and preparation method thereof |
| CN107974869B (en) * | 2017-12-08 | 2020-07-21 | 电子科技大学 | Preparation method of high-orientation high-filling FeSiAl flexible composite paper |
| CN108221465B (en) * | 2017-12-15 | 2020-05-12 | 复旦大学 | Cellulose nano-fiber/carbon fluoride tube flexible composite membrane and preparation method thereof |
| CN109593343B (en) * | 2018-11-12 | 2020-12-29 | 杭州师范大学 | Temperature response flame-retardant film and preparation method and application thereof |
| CN109776829B (en) * | 2019-02-21 | 2021-05-04 | 中国科学院青岛生物能源与过程研究所 | Method for preparing high-strength high-toughness layered structure barrier film |
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| CN103289259A (en) * | 2013-07-01 | 2013-09-11 | 中国石油大学(华东) | High-dielectric composite material containing graphite with layered structure, and preparation method thereof |
| CN103319827A (en) * | 2013-07-02 | 2013-09-25 | 中国科学技术大学 | Method for preparing organic-inorganic nano composite film |
| CN103709565A (en) * | 2013-12-26 | 2014-04-09 | 清华大学 | Composite fiber and polymer based flexible composite film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103289259A (en) * | 2013-07-01 | 2013-09-11 | 中国石油大学(华东) | High-dielectric composite material containing graphite with layered structure, and preparation method thereof |
| CN103319827A (en) * | 2013-07-02 | 2013-09-25 | 中国科学技术大学 | Method for preparing organic-inorganic nano composite film |
| CN103709565A (en) * | 2013-12-26 | 2014-04-09 | 清华大学 | Composite fiber and polymer based flexible composite film and preparation method thereof |
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