CN104231264B - A kind of preparation method and application of graphene oxide/silicon dioxide/polyaniline composite material - Google Patents
A kind of preparation method and application of graphene oxide/silicon dioxide/polyaniline composite material Download PDFInfo
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Abstract
The invention belongs to the crossing domain of organic/inorganic nano complex and functional high molecule material, the performances such as the mechanical strength of graphene oxide itself, conduction, heat conduction are reduced for solving the change of atomic structure of carbon in graphene oxide, thus affecting the performance facilitation to polymer and the problem of final utilization effect, the present invention proposes the preparation method and application of a kind of graphene oxide/silicon dioxide/polyaniline composite material.Described composite is made up of graphene oxide, silicon dioxide and polyaniline three component, the mass percent of three components is respectively graphene oxide 5 ~ 90%, silicon dioxide 5 ~ 90% and polyaniline 5 ~ 90%, by non-covalent functionalization effect, graphene oxide is modified, solve the technical problem that when graphene oxide prepared by existing covalent functionalization method uses as filler, performance is the highest.
Description
Technical field
The invention belongs to the crossing domain of organic/inorganic nano complex and functional high molecule material, be specifically related to
A kind of preparation of the graphene oxide/silicon dioxide/polyaniline composite material with conduction and enhancing dual-use function
Method and application.
Background technology
In organosilicon macromolecule chemical industry, filler is the additive that consumption is maximum, most of organosilicon finished products (bag
Include silicone rubber, silicone oil and silicones) all use mass filler.Such as, conduction is added when manufacturing conductive silicon rubber
White carbon black, graphite, metal make filler, can improve conduction and the thermostability of goods；Organosilicon macromolecule is used as coating
Time, add white or colored filler (such as titanium dioxide, Pulvis Talci, barium sulfate etc.) can improve coating optics,
Process based prediction model；In organosilicon macromolecule, add silicon dioxide, calcium carbonate etc., product can not only be improved
Mechanical property, improve intensity and hardness, but also can effectively reduce cost.Various types of filler typically require through
A certain degree of chemical modification, to improve the interracial contact between organosilicon polymer and the compatibility, thus reaches
To the preferably target such as dispersion, modification.Such as, with silane coupler, filling surface is carried out at covalent functionalization
Reason, can improve the compatibility between filler and matrix, improve filler filling fraction in the base and finished product
Every physical and mechanical properties etc..But, for some filler, the new carbon such as such as graphene oxide,
Although this covalent functionalization is modified and is improved the interracial contact between filler with matrix and phase to a certain extent
Capacitive, but as the change of atomic structure of carbon in graphene oxide is reduced graphene oxide itself
The performances such as mechanical strength, conduction, heat conduction, thus performance facilitation and the final utilization of polymer are imitated by impact
Really.
Summary of the invention
The mechanics reducing graphene oxide itself for solving the change of atomic structure of carbon in graphene oxide is strong
The performances such as degree, conduction, heat conduction, thus impact is to the performance facilitation of polymer and asking of final utilization effect
Topic, the present invention proposes the preparation method and application of a kind of graphene oxide/silicon dioxide/polyaniline composite material.
By non-covalent functionalization effect, graphene oxide is modified, solve prepared by existing covalent functionalization method
The technical problem that when graphene oxide uses as filler, performance is the highest.
The present invention is achieved by the following technical solutions: a kind of graphene oxide/silicon dioxide/polyaniline is combined
Material, described composite is made up of graphene oxide, silicon dioxide and polyaniline three component, three components
Mass percent is respectively graphene oxide 5～90%, silicon dioxide 5～90% and polyaniline 5～90%, three groups
Part sum is 100%.Can by the mass ratio of graphene oxide, silicon dioxide and polyaniline is regulated and controled,
Thus control the power of compounded mix, heat, electrical property.As preferably, the mass percent of three components is respectively oxygen
Functionalized graphene 10～30%, silicon dioxide 30～50% and polyaniline 20～60%.Wherein, described graphite oxide
Alkene is two-dimensional slice structure, sheet number of plies n=1～10, and in graphene oxide, carbon and the mol ratio of oxygen atom are more than 10.
Silicon dioxide is micro nano structure, and polyaniline has zero dimension, one-dimensional or laminated structure, and this different materials is organically
It is combined together to form and there is conduction and strengthen the organic/inorganic compounded mix of dual-use function.
The preparation method of a kind of graphene oxide/silicon dioxide/polyaniline composite material is by graphene oxide, silicon
Source, acid, aniline, initiator and solvent are mixed.
Concrete preparation method is: mixed in mixed solvent in graphene oxide, silicon source in reaction vessel,
Under the conditions of non-neutral 5～90 DEG C stirring reaction 10 minutes～24 hours, extract product obtain graphene oxide/
Silica composite, is then distributed to graphene oxide/silica composite disperse, in solvent, to add
After aniline, acid stir, add initiator at 0～50 DEG C of stirring reaction 10 minutes～4 hours, extraction product
Obtain graphene oxide/silicon dioxide/polyaniline composite material.
Non-neutral condition is that the pH making mixed liquor is not equal to 7；As preferably, the pH value range of mixed liquor is 2
To 12, but pH value is not equal to 7.Regulation pH value can be with acid or alkaline matter, and acid is selected from organic acid (second
Acid, oxalic acid, p-methyl benzenesulfonic acid, citric acid, tartaric acid, glacial acetic acid, oleic acid etc.) or mineral acid (hydrochloric acid,
Nitric acid, sulphuric acid, phosphoric acid, carbonic acid etc.), alkali is selected from organic base (amine, metal alkyl lithium, the alkali metal of alcohol
Salt etc.) or inorganic base (ammonia, soluble alkali metal hydroxide, metal hydroxides, soluble alkaline earth
Metal hydroxides etc.), acid salt (disulfate, hydrophosphate, bicarbonate etc.), basic salt (alkali formula
Curpic carbonate, basic magnesium chloride etc.) etc. in one or more so that described pH value is not equal to 7.For adjusting
The acidity of joint pH value or the concentration of alkaline matter are 1.0 × 10-14～1.0mol/L, as preferably, it is used for regulating
The acidity of pH value or the concentration of alkaline matter are preferably 1.0 × 10-12～1.0 × 10-2mol/L。
Or preparation method is: by graphene oxide, aniline, acid, mixed solvent mixing in reaction vessel,
Add initiator to react 10 minutes～4 hours at 0～50 DEG C in the way of stirring or ultrasound wave induction, extract product
Obtain graphene oxide/Polyaniline, be then distributed to graphene oxide/Polyaniline to disperse molten
In agent, it is acid for adjusting pH after the mixing of addition silicon source, then extracts after 10～90 DEG C of stirrings are reacted 1～12 hour
Product obtains graphene oxide/silicon dioxide/polyaniline composite material.
One or more in organic acid or mineral acid of acid described in above-mentioned preparation method, acid and aniline
Mol ratio is 0.5～4: 1.
Or preparation method is: in reaction vessel, graphene oxide, silicon source, aniline and mixed solvent are mixed
Rear addition acid stirring makes mixed liquor become acid, then adds initiator in mixed liquor, 5～90 DEG C of stirrings
Reaction is carried out 10 minutes～24 hours, extracts product and obtains graphene oxide/silicon dioxide/polyaniline composite material.
One or more in organic acid or mineral acid of described acid, the molal quantity of acid more than or equal to aniline with
The twice of silicon source molal quantity sum,
In 3 kinds of preparation methoies described above, graphene oxide is pressed powder or its dispersion liquid.Graphite oxide
The preparation of alkene dispersion liquid: graphene oxide is made in a solvent concentration more than 1.0 × 10-4The suspension of mg/mL
Liquid, forms graphene oxide dispersion after ultrasonic disperse processes；Described graphene oxide is selected from solid oxide
One in the suspension of Graphene or graphene oxide, the ultrasonic power of ultrasonic disperse is more than 20 watts, the time
More than 10 minutes；The solvent of graphene oxide dispersion is selected from one or both in organic solvent, water.Make
For preferably, described organic solvent is selected from ethanol, ethylene glycol, 1-propanol, isopropanol, n-butyl alcohol, N, N-
Dimethylformamide, ethylenediamine, butanone, acetone, N-Methyl pyrrolidone, ether, Isosorbide-5-Nitrae-dioxane,
Oxolane, toluene, dimethylbenzene, hexamethylene, chloroform, carbon tetrachloride etc. therein one or more.Oxidation
Graphene is 5.5 × 10 with the mass ratio of aniline-2～18: 1, as preferably, the quality of graphene oxide and aniline
Ratio preferably 0.16～1.5: 1.
Described silicon source is selected from silicate class or silicates, as preferably, selected from tetraethyl orthosilicate, positive silicon
One or more in acid four methyl ester, sodium silicate, potassium silicate.Graphene oxide with the mass ratio in silicon source is
1.5×10-2～9: 1, as preferably, graphene oxide is 5.7 × 10 with the mass ratio in silicon source-2～0.5: 1.
Initiator is selected from Ammonium persulfate., ferric chloride, potassium dichromate, potassium chlorate, benzoyl peroxide, dioxy
Changing one or more in manganese, cerous sulfate or hydrogen peroxide, initiator is 0.25～2: 1 with the mol ratio of aniline,
Mixed solvent is selected from water or organic and water mixed solvent, and dispersion solvent is selected from alcohols, water or alcohol and water
Mixed solvent.Mixed solvent participates in the hydrolysis in esters of silicon acis eka-silicon source with the water in dispersion solvent.Organic solvent
Selected from ethanol, ethylene glycol, 1-propanol, isopropanol, n-butyl alcohol, DMF, ethylenediamine, first
Ethyl ketone, acetone, N-Methyl pyrrolidone, ether, Isosorbide-5-Nitrae-dioxane, oxolane, toluene, dimethylbenzene,
Hexamethylene, chloroform, carbon tetrachloride etc. therein one or more.Alcohols is preferably ethanol, ethylene glycol, 1-
Propanol, isopropanol, n-butyl alcohol.Water is more than 4 with the mol ratio in silicon source.
Reaction terminate after, extract product can by select filter, solvent removed by vacuum or centrifugal in the way of, scrubbed
It is dried and obtains graphene oxide/silicon dioxide/polyaniline composite material.
A kind of graphene oxide/silicon dioxide/polyaniline composite material of the present invention is by graphene oxide, titanium dioxide
Silicon and polyaniline three component are made, according to mass fraction meter graphene oxide 5～90%, silicon dioxide 5～90%
With polyaniline 5～90%.Oxygen-containing functional group on graphene oxide lamella can be silicon dioxide and polyaniline
Synthesis provides avtive spot, and when the carbon oxygen atom mol ratio of graphene oxide is too low, its electric conductivity and intensity are equal
Tend to deterioration, it is difficult to meeting the requirement of conduction and reinforcer, in present case, this ratio is with more than 10 relatively
For suitably.When silicon oxide component content in the composite is too low, composite material strength reduces, when two
During silicon oxide component too high levels in the composite, conductivity of composite material reduces.When polyaniline component exists
When content in composite is too low, composite is difficult to obtain good electrical conductivity, when polyaniline component is multiple
During too high levels in condensation material, composite is difficult to obtain higher intensity.When the content of three component materials is fitted
Time middle, graphene oxide mainly disperses in the composite with which floor form of monolayer or minority, can serve as and lead
Electricity body, can serve as again reinforced filling.Silicon dioxide is present in composite with micro-nano form, serves as reinforcement
Body.Silicon dioxide combines with graphene oxide in a supported form, in conjunction with after be remarkably improved and polymerizable organosilicon
The compatibility of thing, the covalent functionalization effectively overcoming all kinds of group modifies the change institute to graphene oxide structure
Degradation problem under the conduction that causes, intensity.Polyaniline presented in nanoparticle, nano wire or lamellar in
In composite, serve as electric conductor.By the introducing of silicon dioxide, enhance composite and organosilicon matrix
The compatibility, improve the intensity of composite；By the introducing of electrically conductive polyaniline, can effectively make up titanium dioxide
The deficiency that silicon electric conductivity is not good enough, improves the electric conductivity of composite.The material of these three different component is by multiple
Close and define the compounded mix with conduction and reinforcement dual-use function.
Graphene oxide/silicon dioxide/polyaniline composite material of the present invention is in the enhancing of organosilicon polymer
With the application on conductive filler, have graphene oxide/silicon dioxide/polyaniline composite material adds to during use
In organosilicon polymer.
Compared with prior art, the invention has the beneficial effects as follows:
(1) composite of the present invention has good electric conductivity and certain intensity, makes composite have conduction
With reinforcement dual-use function；
(2) composite of the present invention is for single graphene oxide, has higher electric conductivity with strong
Degree, and between organosilicon polymer, have the more preferable compatibility, it is more suitable for mending as the conduction of organosilicon polymer
Strong filler；
(3) preparation method is simple, and safe preparation process, energy consumption is low, workable.
Detailed description of the invention
Below by embodiment, the present invention is further elaborated.
Embodiment 1:
(1) in reaction vessel by the aqueous dispersions of 288mL graphene oxide (containing graphene oxide 0.288g,
Aqueous 288g, 16mol), 5g tetraethyl orthosilicate (2.4 × 10-2Mol) mix homogeneously, adds hydroxide
Sodium makes mixed liquor pH value be 12,15 DEG C of stirring reactions 12 hours, filters, washs, is dried acquisition oxidation
Graphene/silicon dioxide composite.
(2) product of step (1) is distributed in ethylene glycol, adds 1.152g aniline (1.24 × 10-2mol)、
0.633g concentrated sulphuric acid (6.2 × 10-3After mol stirs, add 5.659g Ammonium persulfate. (2.48 × 10-2mol)
0 DEG C (ice-water bath) stirring reaction 4 hours, filter, wash, be dried to obtain graphene oxide/silicon dioxide
/ polyaniline composite material.
In the composite that the present embodiment 1 obtains, the conversion ratio of tetraethyl orthosilicate and aniline is approximately equal to
100%, in product, the quality of graphene oxide is about: 0.288g, and the quality of silicon dioxide is about 1.44g,
The quality of polyaniline is about 1.152g, and wherein the mass fraction of graphene oxide is about: 10%, silicon dioxide
Mass fraction be about 50%, the mass fraction of polyaniline is about 40%.
Embodiment 2:
(1) in reaction vessel by the alcohol dispersion liquid (containing graphene oxide 6g) of 6000mL graphene oxide,
12.195g sodium silicate (0.1mol), 50g water (2.8mol) mix homogeneously, add 8.719g nitric acid (0.2
Mol) it is acid for making mixed liquor, 80 DEG C of stirring reactions 10 minutes, filters, washs, is dried acquisition oxidation
Graphene/silicon dioxide composite.
(2) product of step (1) is distributed in isopropanol, adds 8g aniline (8.59 × 10-2mol)、33.935
G concentrated hydrochloric acid (after 0.344mol stirs, adds 3.738g manganese dioxide (4.30 × 10-2Mol) 50
DEG C stirring reaction 10 minutes, filter, wash, be dried to obtain graphene oxide/silicon dioxide/polyaniline be combined
Material.
In the composite that the present embodiment 2 obtains, the conversion ratio of sodium silicate and aniline is approximately equal to 100%, product
The quality of middle graphene oxide is about: 6g, the quality of silicon dioxide is about 6g, and the quality of polyaniline is big
Being about 8g, wherein the mass fraction of graphene oxide is about: 30%, and the mass fraction of silicon dioxide is about 30%,
The mass fraction of polyaniline is about 40%.
Embodiment 3:
(1) in reaction vessel, the DMF dispersion liquid of 1397mL graphene oxide (is contained oxidation
Graphene 1.397g), 0.9313g aniline (0.01mol), 1.722g p-methyl benzenesulfonic acid (0.01mol) mix
Close uniformly, add 1.133g30% hydrogen peroxide (0.01mol) and react 4 hours 5 DEG C of stirrings, be centrifuged, wash
Wash, be dried to obtain graphene oxide/polyaniline composite material.
(2), during the product to (1) is distributed to 200mL ethanol, the positive quanmethyl silicate of 5.909g (3.88 is added
×10-2Mol), 10g water (0.556mol), 15.8g sulphuric acid (0.155mol) make mixed liquor be acid,
10 DEG C of stirring reactions 12 hours, filter, wash, be dried acquisition graphene oxide/silicon dioxide/polyaniline
Composite.
In the composite that the present embodiment 3 obtains, the conversion ratio of positive quanmethyl silicate and aniline is approximately equal to
100%, in product, the quality of graphene oxide is about: 1.397g, the quality of silicon dioxide is about 2.328
G, the quality of polyaniline is about 0.9313g, and wherein the mass fraction of graphene oxide is about: 30%, dioxy
The mass fraction of SiClx is about 50%, and the mass fraction of polyaniline is about 20%.
Embodiment 4:
(1) by N-Methyl pyrrolidone dispersion liquid (the oxygen-containing fossil of 596mL graphene oxide in reaction vessel
Ink alkene 0.596g), 3.725g aniline (0.04mol), 4.804g acetic acid (0.08mol) mix homogeneously, add
Enter 1.225g potassium chlorate (0.01mol) to react 10 minutes 50 DEG C of stirrings, be centrifuged, wash, be dried to obtain
Graphene oxide/polyaniline composite material.
(2), during the product to (1) is distributed to 100g water (5.556mol), 4.852g potassium silicate (3.14 is added
×10-2Mol), 5.65g oxalic acid (6.28 × 10-2Mol) it is acid for making mixed liquor, stirs reaction 1 at 90 DEG C
Hour, filter, wash, be dried acquisition graphene oxide/silicon dioxide/polyaniline composite material.
In the composite that the present embodiment 4 obtains, the conversion ratio of potassium silicate and aniline is approximately equal to 100%, product
The quality of middle graphene oxide is about: 0.596g, the quality of silicon dioxide is about 1.887g, polyaniline
Quality be about 3.725g, wherein the mass fraction of graphene oxide be about: 10%, the quality of silicon dioxide
Mark is about 30%, and the mass fraction of polyaniline is about 60%.
Embodiment 5:
(1) in reaction vessel by the toluene dispersion liquid (containing graphene oxide 1g) of 1000mL graphene oxide,
8.1g tetraethyl orthosilicate (3.89 × 10-2Mol), 18g water (1mol), 81.6g concentrated sulphuric acid (0.8mol)
With 3.333g aniline (3.58 × 10-2Mol) mix homogeneously makes reaction composite.
(2) in (1), 2.919g anhydrous ferric trichloride (1.8 × 10 is added-2Mol), 90 DEG C of stirrings react into
Row 1 hour, is centrifuged, washs, is dried to obtain graphene oxide/silicon dioxide/polyaniline composite material.
In the composite that the present embodiment 5 obtains, the conversion ratio of tetraethyl orthosilicate and aniline is approximately equal to
100%, in product, the quality of graphene oxide is about: 1g, and the quality of silicon dioxide is about 2.333g,
The quality of polyaniline is about 3.333g, and wherein the mass fraction of graphene oxide is about: 15%, silicon dioxide
Mass fraction be about 35%, the mass fraction of polyaniline is about 50%.
Embodiment 6:
(1) in reaction vessel by the aqueous dispersions (containing graphene oxide 1g) of 1000mL graphene oxide, 3.659
G sodium silicate (2.99 × 10-2Mol), 9g water (0.5mol), 7.7g oxalic acid (0.128mol) and 1.2g
Aniline (1.29 × 10-2Mol) mix homogeneously makes reaction mixture.
(2) in (1), 3.795g potassium dichromate (1.29 × 10 is added-2Mol), carry out 5 DEG C of stirring reactions
24 hours, it is centrifuged, washs, is dried to obtain graphene oxide/silicon dioxide/polyaniline composite material.
In the composite that the present embodiment 6 obtains, the conversion ratio of sodium silicate and aniline is approximately equal to 100%, product
The quality of middle graphene oxide is about: 1g, the quality of silicon dioxide is about 1.8g, the quality of polyaniline
Being about 1.2g, wherein the mass fraction of graphene oxide is about: 25%, and the mass fraction of silicon dioxide is about
Being 45%, the mass fraction of polyaniline is about 30%.
Application examples
Graphene oxide/silicon dioxide/polyaniline composite material obtained by embodiment 1～6 is filled into terminal hydroxy group
In polydimethylsiloxane (viscosity 5000cp) matrix, add tetraethyl orthosilicate, dilaurate dibutyl
After the crosslinked solidification of stannum, the performance test results is as shown in table 1.
Table 1: the performance test results
Claims (9)
1. graphene oxide/silicon dioxide/polyaniline composite material, it is characterized in that, described composite is made up of graphene oxide, silicon dioxide and polyaniline three component, the mass percent of three components is respectively graphene oxide 5 ~ 90%, silicon dioxide 5 ~ 90% and polyaniline 5 ~ 90%, three component sums are 100%
The preparation method of described composite is for be mixed by graphene oxide, silicon source, acid, aniline, initiator and solvent.
2. the preparation method of a kind of graphene oxide/silicon dioxide/polyaniline composite material as claimed in claim 1, it is characterised in that described preparation method is for be mixed by graphene oxide, silicon source, acid, aniline, initiator and solvent.
The preparation method of a kind of graphene oxide/silicon dioxide/polyaniline composite material the most according to claim 2, it is characterized in that, by graphene oxide in reaction vessel, silicon source mixes in mixed solvent, under the conditions of non-neutral, 5 ~ 90 DEG C of stirrings are reacted 10 minutes ~ 24 hours, extract product and obtain graphene oxide/silica composite, then it is distributed to graphene oxide/silica composite disperse in solvent, add aniline, after acid stirs, add initiator 0 ~ 50 DEG C of stirring reaction 10 minutes ~ 4 hours, extract product and obtain graphene oxide/silicon dioxide/polyaniline composite material.
The preparation method of a kind of graphene oxide/silicon dioxide/polyaniline composite material the most according to claim 2, it is characterized in that, by graphene oxide in reaction vessel, aniline, acid, mixed solvent mixes, add initiator to react 10 minutes ~ 4 hours at 0 ~ 50 DEG C in the way of stirring or ultrasound wave induction, extract product and obtain graphene oxide/Polyaniline, then it is distributed to graphene oxide/Polyaniline disperse in solvent, it is acid for adjusting pH after adding the mixing of silicon source, extract product after stirring reactions 1 ~ 12 hour at 10 ~ 90 DEG C again and obtain graphene oxide/silicon dioxide/polyaniline composite material.
The preparation method of a kind of graphene oxide/silicon dioxide/polyaniline composite material the most according to claim 2, it is characterized in that, adding acid stirring after graphene oxide, silicon source, aniline and mixed solvent being mixed in reaction vessel makes mixed liquor become acid, then in mixed liquor, add initiator, carry out 10 minutes ~ 24 hours 5 ~ 90 DEG C of stirring reactions, extract product and obtain graphene oxide/silicon dioxide/polyaniline composite material.
6. according to the preparation method of graphene oxide/silicon dioxide/polyaniline composite material a kind of according to any one of claim 2 ~ 5, it is characterized in that, described graphene oxide is pressed powder or its dispersion liquid, silicon source is selected from silicate class or silicates, one or more in organic acid or mineral acid of acid, initiator is selected from Ammonium persulfate., ferric chloride, potassium dichromate, potassium chlorate, benzoyl peroxide, manganese dioxide, one or more in cerous sulfate or hydrogen peroxide, mixed solvent is selected from the mixed solvent of water or organic solvent and water, dispersion solvent is selected from alcohols, the mixed solvent of water or alcohol and water.
The preparation method of a kind of graphene oxide/silicon dioxide/polyaniline composite material the most according to claim 6, it is characterised in that graphene oxide is 5.5 × 10 with the mass ratio of aniline-2~ 18:1, graphene oxide is 1.5 × 10 with the mass ratio in silicon source-2~ 9:1, initiator is 0.25 ~ 2:1 with the mol ratio of aniline, and the consumption that mol ratio is 0.5 ~ 4:1 or acid of acid and aniline is more than or equal to the twice of aniline with silicon source molal quantity sum, and in reaction, water and the mol ratio in silicon source are more than 4.
8. graphene oxide/silicon dioxide/polyaniline composite material as claimed in claim 1 application in the enhancing and conductive filler of organosilicon polymer.
The application of graphene oxide/silicon dioxide/polyaniline composite material the most according to claim 8, it is characterised in that during use, graphene oxide/silicon dioxide/polyaniline composite material is added in organosilicon polymer.
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| CN102676044B (en) * | 2012-05-16 | 2014-04-02 | 沈阳化工大学 | Preparation method for polyaniline silica anti-corrosion coating |
| CN103144388B (en) * | 2013-03-21 | 2015-06-17 | 四川农业大学 | Preparation method and application of polyaniline/titanium dioxide/graphene conductive composite membrane |
| CN103524785B (en) * | 2013-07-30 | 2015-09-09 | 杭州师范大学 | A kind of Graphene/SiO 2matrix material and preparation method thereof and application |
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