CN104610572B - Amino polystyrene functionalization graphene nano material and preparation method thereof - Google Patents
Amino polystyrene functionalization graphene nano material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of amino polystyrene functionalization graphene nano material and preparation method thereof.The functionalization graphene nano material is a kind of organic covalent nucleophilic addition of science integration, and amide condensed and non-covalent electrostatic self-assembled synchronizing function technology modifies amino polystyrene in the built-up nano hybridization structure of surface of graphene oxide and edge.Preparation process mainly includes the preparation of graphite oxide and two steps of preparation of functionalization graphene nano-hybrid material.The hybrid material thermal stability that the present invention synthesizes is improved a lot than graphene oxide, and the covering amount of surface of graphene oxide amino polystyrene can be adjusted by the change of reaction temperature.Along with synthesis step is simple, efficient, it is easy to largely prepare, is particularly suitable for application as flame-retardant materials and its polymer-base flame-proof nano composite material.Therefore the nano material also has preferable application prospect and economic benefit.
Description
Technical field
The present invention relates to a kind of functionalization graphene nano material and preparation method thereof, particularly a kind of amino polystyrene
Functionalization graphene nano material and preparation method thereof, belongs to field of material preparation.
Background technology
Graphene (Graphene) has come from its excellent performance since 2004 are found, and has become new material neck
The dazzling star's material in one, domain.In recent years, constantly break through multiple bottleneck problems, composite, energy storage with
The field such as conversion and biology obtains one and another important achievement.Research based on graphene has turned into world technology innovation
One of Disciplinary Frontiers.
At present, in addition to the CVD method except price costly can be with macroscopic preparation of graphene, another important method is graphite
Deep oxidation prepare graphite oxide, then by reducing macroscopic preparation of graphene and its derivative.This also turns into more cheap
The important wet chemical method of macroscopic preparation of graphene.However, stronger Van der Waals masterpiece between the graphene layer of structural integrity be present
With, and surface is in chemical inertness, is easily reunited；Also, the reduced graphene of any modification is not added to reunite again as stone yet
Ink, this also more limits the application in polymer nanocomposites.Therefore, carry out and be based on important presoma, aoxidize stone
Ink, covalent and non-covalent functionalization be play its excellent properties, the important prerequisite applied to each field.This be also it is current, extensively
The wet-chemical strategy of general use.
As the method for one typical from top to bottom (top-down), the chemical modification based on graphene oxide still by
Be considered at present most rationally, cost is relatively low, easy modification and can largely prepare a kind of effective means of functionalization graphene.Oxidation
Graphenic surface is thermally labile material rich in oxygen-containing functional group, heated easily to degrade, and weightless temperature section is very
It is narrow.Thus, realize that functionalization graphene has polymolecularity and high thermal stability concurrently by covalently or non-covalently chemical modification technology
Etc. a series of problem in science, also turn into one of work that is most important at present and most challenging.
Up to now, the wet chemistry modification based on graphite oxide is broadly divided into organic covalent and non-covalent two kinds of strategies.
For example, covalent functionalization mainly includes isocyanic acid ester process, esterification, amidatioon, silanization method, nucleophilic displacement of fluorine and phase transfer of technology
Deng.Non-covalent functionalization mainly includes H-bonding self-assembly, electrostatic self-assembled and Host-guest Recognition etc..Nanometer material by functionalization
Material, can make its performance be significantly improved.By taking heat endurance as an example, after introducing molecule, because changing interfacial interaction, work(
Material property can be changed and be significantly better than graphite oxide.(1.Zhang S P,Song H O,Supramolecular graphene
oxide-alkylamine hybrid materials:variation of dispersibility and improvment
of thermal stability,New Journal of Chemistry.,2012,36(9):1693-1908.2.Zhang S
P,Xiong P,Yang X J,Wang X.Novel PEG functionalized graphene nanosheets:
enhancement of dispersibility and thermal stability,Nanoscale,2011,3(5):2169-
2174.)
But method is different from the method that the present invention uses used by the above-mentioned methods, prepared by material.Usually, document
The reaction based on GO oxy radicals of middle report is mostly single covalently or non-covalently strategy.Reagent one used in operating process
As exist or the defects of toxicity is big or easily meets water decomposition.Synthesis step is cumbersome, it is difficult to industrialization large-scale production.
The content of the invention
The present invention is directed to the deficiencies of reaction temperature existing for prior art is high, cumbersome, coupling reagent toxicity is larger, carries
For a kind of amino polystyrene functionalization graphene nano material.
It is a further object of the present invention to provide a kind of preparation method of amino polystyrene functionalization graphene nano material.
The technical solution for realizing the object of the invention is：A kind of amino polystyrene functionalization graphene nano material,
Its general structure is：
A kind of preparation method of amino polystyrene functionalization graphene nano material, by by natural graphite powder depth oxygen
Change handles to obtain oxidation graphite solid, then through the ultrasonic disperse in DMF (DMF), obtains graphene oxide
DMF dispersion liquids, after adding amino polystyrene, after stirring, filtering and dry, obtain functionalization graphene hybrid material.
Its specific technique comprises the following steps：
Step 1, the Hummers methods after improvement are used to prepare oxidation graphite solid (GO) with natural graphite powder；
Under step 2, ultrasound, prepare the DMF suspension of graphene oxide, the ratio of graphite oxide and DMF solvent for 7.5~
15mg/mL；
Step 3, prepare amination polystyrene (PPAS) DMF solution；
Step 4, the suspension of step 2 mixed with the PPAS solution of step 3, graphene oxide and PPAS mass ratio
For 1：10~10：1, it is heated to 100~160 DEG C of stirrings；
Step 5, it is filtered under diminished pressure, washs, obtaining amino polystyrene functionalization graphene nano material after drying
(PPAS-GO)。
Ultrasonic time described in step 2 is 2~10h.
The ratio of PPAS and DMF solvent described in step 3 are 1：10~1:500g/mL；Described whipping temp scope is
25~80 DEG C.
Reaction time described in step 4 is 0.5~3 day.
Compared with prior art, the preparation method of amino polystyrene functionalization graphene nano material provided by the invention
Avoid using thionyl chloride, isocyanates, N, N- Dicyclohexylcarbodiimides (DCC) etc. with virose organic coupling agent.And
It is that under agitation, first using one pot of covalent and non-covalent synchronized compound technology, only by simply stirring, filtering etc. is often
Rule operation, you can be prepared.The functionalization graphene nano material that simultaneously prepared by the present invention can easily pass through tune
Load capacity of the reaction temperature control amino polystyrene on GO is saved, and then adjusts the thermal stability of hybrid material.PS segments
Introducing be effectively improved GO thermal stability, while improve the interface compatibility between polymeric matrix, make it more
The thermal stability for improving polymer composites advantageous as Nano filling is added to build novel anti-flammability nano composite material.
The preparation method of the present invention presses close to the requirement of Green Chemistry, and compared with low-temperature operation, it is easily controllable, be advantageous to industrial mass life
Production.
Embodiments of the invention are described in further detail below in conjunction with the accompanying drawings.
Brief description of the drawings
Fig. 1 is the preparation process schematic diagram of functionalization graphene nano material prepared by the present invention.
Fig. 2 is the infrared spectrogram of the functionalization graphene nano material synthesized in the embodiment of the present invention 1.
Fig. 3 is the infrared spectrogram of the functionalization graphene nano material synthesized in the embodiment of the present invention 3.
Fig. 4 is that the thermostabilization analysis of the functionalization graphene nano material synthesized in invention embodiment 1 and 3 is bent
Line.
Embodiment
Embodiments of the invention are described in further detail below in conjunction with the accompanying drawings, the present embodiment is with the technology of the present invention side
Implemented under the premise of case, give detailed embodiment and specific operating process, but protection scope of the present invention is unlimited
In following embodiments.
As shown in figure 1, a kind of amino polystyrene functionalization graphene nano material and preparation method thereof, this method includes
Following steps：
Step 1, the Hummers methods after improvement are used to prepare oxidation graphite solid with natural graphite powder；
Step 2,2~10h of ultrasound, prepare the DMF suspension of graphene oxide, and the ratio of graphite oxide and DMF solvent is 7.5
~15mg/mL；
The ratio of step 3, the DMF solution for preparing PPAS, PPAS and DMF solvent is 1：10~1:500g/mL, whipping temp model
Enclose for 25~80 DEG C；
Step 4, the suspension of step 2 mixed with the PPAS solution of step 3, graphene oxide and PPAS mass ratio
For 1：10~10：1,100~160 DEG C of stirrings are heated to, the reaction time is 0.5~3 day；
Step 5, it is filtered under diminished pressure, washs, obtaining amino polystyrene functionalization graphene nano material after drying.
Embodiment 1
The first step, the preparation of oxidation graphite solid；
At 80 DEG C, after with the 30mL concentrated sulfuric acids, 10g potassium peroxydisulfates and 10g phosphorus pentoxides, 20g native graphites are pre-oxidized,
PH=7 is washed to, air drying is stand-by overnight；
The 460mL concentrated sulfuric acids are cooled to 0 DEG C or so, then the 20g graphite pre-oxidized is added thereto, is slowly added into
60g potassium permanganate so that system temperature is no more than 20 DEG C, and 35 DEG C are warming up to after addition, after stirring 2h, and in batches slowly
Add 920mL deionized waters so that system temperature be no more than 98 DEG C, be stirred for after 15 minutes, add 2.8L deionized waters and
The hydrogen peroxide of 50mL 30%.Obtained glassy yellow suspension is depressurized and filtered, washing.Until there is no sulfate ion in filtrate,
And when being in neutral, product is dried in 60 DEG C of vacuum, obtains oxidation graphite solid；
Second step, 50mg graphite oxides powder is loaded into round-bottomed flask, adds 15mL DMFs
(DMF) solvent, after ultrasonic 5h, the suspension of graphene oxide is obtained；
3rd step, take 0.1g PPAS to be dissolved at room temperature in 5mLDMF, prepare PPAS DMF solution；
4th step, the PPAS solution in the 3rd step is slowly dropped to the GO suspension prepared in second step, is heated to 100
DEG C, it is stirred vigorously 1 day；
5th step, by the crude product that the 4th step obtains through filtering, washing, after drying, produce product PPAS-GO100.
The infrared spectrum of functionalization graphene nano material in a solvent is as shown in Figure 2, it was demonstrated that the nano-hybrid material is
Success synthesizes.
Heat endurance is as shown in figure 4, the thermal stability of functionalization graphene nano material is higher than unmodified oxidation stone
Black alkene.
Embodiment 2
First to the 3rd step, with step 1 in embodiment 1 to three.
4th step, the PPAS solution in the 3rd step is slowly dropped to the GO suspension prepared in second step, is heated to 110
DEG C, it is stirred vigorously 1 day；
5th step, with step 5 in embodiment 1.
Embodiment 3
First to the 3rd step, with step 1 in embodiment 1 to three.
4th step, the PPAS solution in the 3rd step is slowly dropped to the GO suspension prepared in second step, is heated to 120
DEG C, it is stirred vigorously 1 day；
5th step, by the crude product that the 4th step obtains through filtering, washing, after drying, produce product PPAS-GO120.
The infrared spectrum of functionalization graphene nano material in a solvent is as shown in Figure 3, it was demonstrated that the nano-hybrid material is
Success synthesizes.
Heat endurance is as shown in figure 4, the thermal stability of functionalization graphene nano material is higher than unmodified oxidation stone
Black alkene.
Embodiment 4
First to the 3rd step, with step 1 in embodiment 1 to three.
4th step, the PPAS solution in the 3rd step is slowly dropped to the GO suspension prepared in second step, is heated to 130
DEG C, it is stirred vigorously 1 day；
5th step, with step 5 in embodiment 1.
Embodiment 5
First to the 3rd step, with step 1 in embodiment 1 to three.
4th step, the PPAS solution in the 3rd step is slowly dropped to the GO suspension prepared in second step, is heated to 140
DEG C, it is stirred vigorously 1 day；
5th step, with step 5 in embodiment 1.
Embodiment 6
First to the 3rd step, with step 1 in embodiment 1 to three.
4th step, the PPAS solution in the 3rd step is slowly dropped to the GO suspension prepared in second step, is heated to 150
DEG C, it is stirred vigorously 1 day；
5th step, with step 5 in embodiment 1.
Embodiment 7
First to the 3rd step, with step 1 in embodiment 1 to three.
4th step, the PPAS solution in the 3rd step is slowly dropped to the GO suspension prepared in second step, is heated to 160
DEG C, it is stirred vigorously 1 day；
5th step, with step 5 in embodiment 1.
Embodiment 8
The first step, with step 1 in embodiment 1.
Second step, 50mg graphite oxides powder is loaded into round-bottomed flask, adds 6.67mL DMFs
(DMF) solvent, after ultrasonic 2h, the suspension of graphene oxide is obtained；
3rd step, take 0.1g PPAS to be dissolved at 80 DEG C in 1mL DMF, prepare PPAS DMF solution；
4th step, the PPAS solution in the 3rd step is slowly dropped to the GO suspension prepared in second step, is heated to 100
DEG C, it is stirred vigorously 3 days；
5th step, by the crude product that the 4th step obtains through filtering, washing, after drying, produce product.
Embodiment 9
The first step, with step 1 in embodiment 1.
Second step, 50mg graphite oxides powder is loaded into round-bottomed flask, adds 3.33mL DMFs
(DMF) solvent, after ultrasonic 10h, the suspension of graphene oxide is obtained；
3rd step, take 0.1g PPAS to be dissolved at 30 DEG C in 50mL DMF, prepare PPAS DMF solution；
4th step, the PPAS solution in the 3rd step is slowly dropped to the GO suspension prepared in second step, is heated to 120
DEG C, it is stirred vigorously 2 days；
5th step, by the crude product that the 4th step obtains through filtering, washing, after drying, produce product.
Embodiment 10
First to second step, with step 1 in embodiment 1 to two.
3rd step, the PPAS solution in the 3rd step is slowly dropped to the GO suspension prepared in second step, is heated to 150
DEG C, it is stirred vigorously 1 day；
Four to five step, with step 4 in embodiment 1 to five.
Embodiment 11
The first step, with step 1 in embodiment 1.
Second step, 50mg graphite oxides powder is loaded into round-bottomed flask, adds 15mL DMFs
(DMF) solvent, after ultrasonic 7h, the suspension of graphene oxide is obtained；
3rd step, take 0.5g PPAS to be dissolved at 30 DEG C in 40mL DMF, prepare PPAS DMF solution；
4th step, the PPAS solution in the 3rd step is slowly dropped to the GO suspension prepared in second step, is heated to 100
DEG C, it is stirred vigorously 1 day；
5th step, by the crude product that the 4th step obtains through filtering, washing, after drying, produce product.
Embodiment 12
The first step, with step 1 in embodiment 1.
Second step, 50mg graphite oxides powder is loaded into round-bottomed flask, adds 20mL DMFs
(DMF) solvent, after ultrasonic 5h, the suspension of graphene oxide is obtained；
3rd step, take 0.05g PPAS to be dissolved at 40 DEG C in 10mL DMF, prepare PPAS DMF solution；
4th step, the PPAS solution in the 3rd step is slowly dropped to the GO suspension prepared in second step, is heated to 150
DEG C, it is stirred vigorously 0.5 day；
5th step, with step 5 in embodiment 1.
Embodiment 13
The first step, with step 1 in embodiment 1.
Second step, 50mg graphite oxides powder is loaded into round-bottomed flask, adds 10mL DMFs
(DMF) solvent, after ultrasonic 6h, the suspension of graphene oxide is obtained；
3rd step, take 0.05g PPAS to be dissolved at 25 DEG C in 25mL DMF, prepare PPAS DMF solution；
4th step, the PPAS solution in the 3rd step is slowly dropped to the GO suspension prepared in second step, is heated to 120
DEG C, it is stirred vigorously 1 day；
5th step, with step 5 in embodiment 1.
The present invention abandons the organic coupling agents such as the larger isocyanates of toxicity, thionyl chloride, but science integration is organic common
Valency nucleophilic addition, amide condensed and non-covalent electrostatic self-assembled synchronizing function technology modify amino polystyrene in oxidation stone
The built-up nano hybridization structure in black alkene surface and edge.Preparation process mainly includes preparation and the function fossil of graphite oxide
Two steps of preparation of black alkene nano-hybrid material.The hybrid material thermal stability that the present invention synthesizes has very than graphene oxide
It is big to improve, and the covering amount of surface of graphene oxide amino polystyrene can be adjusted by the change of reaction temperature.Add
Synthesis step is simple, efficient, is easy to largely prepare, is particularly suitable for application as flame-retardant materials and its polymer-base flame-proof nanometer is answered
Condensation material.
Claims (4)
1. a kind of preparation method of amino polystyrene functionalization graphene nano material, it is characterised in that comprise the following steps：
Step 1, the Hummers methods after improvement are used to prepare oxidation graphite solid with natural graphite powder；
Under step 2, ultrasound, the DMF suspension of graphene oxide is prepared, the ratio of graphite oxide and DMF solvent is 7.5 ~ 15 mg/
mL；
Step 3, the DMF solution for preparing PPAS；
Step 4, the suspension of step 2 mixed with the PPAS solution of step 3, graphene oxide and PPAS mass ratio are
1：10~10：1, it is heated to 100 ~ 160 DEG C of stirring reactions；
Step 5, it is filtered under diminished pressure, washs, obtaining amino polystyrene functionalization graphene nano material after drying.
2. the preparation method of amino polystyrene functionalization graphene nano material according to claim 1, its feature exist
In in step 2, described ultrasonic time is 2 ~ 10h.
3. the preparation method of amino polystyrene functionalization graphene nano material according to claim 1, its feature exist
In in step 3, the ratio of PPAS and DMF solvent is 1：10~1:500 g/mL, the whipping temp scope of solution is 25 ~ 80 DEG C.
4. the preparation method of amino polystyrene functionalization graphene nano material according to claim 1, its feature exist
In in step 4, the described stirring reaction time is 0.5 ~ 3 day.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102431997A (en) * | 2011-09-07 | 2012-05-02 | 南京师范大学 | Graphene oxide with antibacterial and anticoagulant functions and preparation method thereof |
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Non-Patent Citations (2)
| Title |
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| Influence of Processing Technique on the Physical Properties of Modified Polystyrene/Exfoliated Graphite Nanocomposites;Ayesha Kausar, et al.;《Materials and Manufacturing Processes》;20150106;第30卷(第3期);正文第347页右栏第1段 * |
| 超声辅助Hummers法制备氧化石墨烯;邹正光 等;《无机化学学报》;20110930;第27卷(第9期);正文第1754页第1.2.2节 * |
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