CN104592660B - Polystyrene is multilayer functionalization graphene nano-hybrid material of hinge and preparation method thereof - Google Patents
Polystyrene is multilayer functionalization graphene nano-hybrid material of hinge and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of polystyrene is multilayer functionalization graphene nano-hybrid material of hinge and preparation method thereof.The covalent and non-covalent organic decoration technology of combination of sciences of the present invention, one pot of nano-hybrid material constructed with thermal stability enhancement effect, and the load capacity of PS on hybrid material can be adjusted by changing cyclodextrin species and reaction temperature；The functionalization and hybridization materials synthesis step is simple, efficient, simple in after-treatment, it is easy to a large amount of preparations.Polystyrene is a kind of quite varied polymer of application, can be widely used for light industry, electrically etc. field is used as insulating materials, heat-insulating heat-preserving material, transparent membrane, capacitor dielectric layer etc..But also simultaneously existence is crisp and the low significant drawback of heat resistance.The present invention as hinge, will be greatly increased the compatibility of the grapheme material and PS, there is potential using value in field of compound material by PS；It is particularly suitable for use as Nano filling and prepares heat resistant type flame-retardant polymer nano composite material.
Description
Technical field
The present invention relates to a kind of polystyrene (PS) multilayer functionalization graphene nano-hybrid material and its system for hinge
Preparation Method, the enhanced PS of particularly a kind of heat endurance for one pot of chemical modification graphene oxide of hinge nano-hybrid material and
Its preparation method, belongs to field of material preparation.
Background technology
Since Graphene (Graphene) was found from 2004, its excellent physical and chemical performance is come from, received complete
The concern of world research person.Six side's honeycomb two-dimension nano materials that complete Graphene is made up of individual layer carbon atom.Due to
Its surface does not contain functional groups, and therefore Graphene is neither hydrophilic nor oleophylic, hardly disperses in a solvent, therefore it is difficult to
Apply in polymer nanocomposites, it is difficult to industrial mass production.
In order to improve the surface nature and compatibility with other matrixes of Graphene, the change with graphene oxide as presoma
The extensive research and development that covalent and non-covalent functionalization technology of preparing has been obtained for scholars are learned, and has become indispensable weight
Want one of method.
Graphene oxide (Graphene oxide, GO) is generally by classical improved Hummers deep oxidations method
It is prepared and obtains.As its surface and edge contain substantial amounts of hydroxyl, epoxy radicals, the oxygen-containing functional group of carboxyl isoreactivity
(according to Lerf-Klinowski models), further can carry out chemical reaction with other molecules, be conducive to magnanimity to prepare function
Graphite alkene.
However, the oxy radical on GO surfaces makes its heat endurance low, it is heated, weightless temperature interval is narrow.Various countries
Researcher has had been built up different types of functionalization graphene nano material, mainly includes isocyanic acid ester process, esterification, acid amides
Change, silanization method, nucleophilic displacement of fluorine and phase transfer of technology etc..Realize that functionalization graphene has polymolecularity and high thermal stability etc. concurrently
A series of problem in science, also become one of work that is most important at present and most challenging.(1.Niyogi S,Bekyarova E,
Itkis M E,et al.Solution Properties of Graphite and Graphene.J.Am.Chem.Soc.,
2006,128(24):7720～7721.2.Zhang SP, Xiong P, Yang, XJ, Wang, X.Novel PEG
functionalized graphene nanosheets:enhancement of dispersibility and thermal
stability.Nanoscale,2011,3:2169-2174.).
But covalent functionalization mostly is using the reaction of the Surface oxygen-containing groups based on GO mainly in document in the above-mentioned methods,
Or non-covalent functionalization.In building-up process, step is various, cumbersome, and pollution is high, it is difficult to industrialization large-scale production.And
Non-covalent functionalization research is relatively fewer, and many claddings for carrying out GO using polymer macromolecule, building-up process in building-up process
In, less with covalent modification, performance of control is poor.The hybrid material of new special construction is especially prepared, is frequently encountered and is passed through
General synthetic routes hardly result in the awkward situation of final product.
Content of the invention
The present invention is for reaction temperature that prior art is present is high, cumbersome, the deficiency such as step is various；Particularly by pressing
Portion with regard to class synthetic route cannot get target product in the case of, there is provided a kind of polystyrene (PS) for hinge multilayer functionalization
Graphene nano hybrid material.
It is a further object of the present invention to provide multilayer functionalization graphene nano hybridization material of the polystyrene (PS) for hinge
The preparation method of material.
The technical solution for realizing the object of the invention is：Polystyrene (PS) is received for the multilayer functionalization graphene of hinge
Rice hybrid material, its general structure are as follows：
Above-mentioned polystyrene (PS) passes through natural graphite powder for the multilayer functionalization graphene nano-hybrid material of hinge
The process of depth Strong oxdiative obtains oxidation graphite solid, then passes through ultrasonic disperse in DMF (DMF), is aoxidized
Graphene DMF dispersion liquids, after activated carboxylic, after adding the cyclodextrin (CDs) and PS of DMF dissolvings, heating stirring, filtration and drying
Afterwards, the multilayer functionalization graphene nano-hybrid material that polystyrene (PS) is hinge is obtained.
Its specific technique is comprised the following steps：
Step 1, with natural flake graphite powder prepare oxidation graphite solid；
Step 2, ultrasound under, prepare graphene oxide DMF suspension, graphite oxide and DMF solvent ratio be 7.5～
15mg/mL；
Step 3, the graphene oxide GOCl for preparing activated carboxylic；
Step 4, the DMF solution for preparing CDs and PS, the mass ratio of CDs and PS is (50：1)～(1：50), CDs and DMF
Than for 0.67～120mg/mL；
Step 5, the GOCl for obtaining step 3 are mixed with the DMF solution of the CD and PS that prepare in step 4, and heating stirring is anti-
Should, wherein, graphene oxide is (30 with the mass ratio of CDs：1)～(1：30)；
Step 6, filtration under diminished pressure, washing, obtain functionalization graphene nano-hybrid material after drying.
Oxidation graphite solid described in step 1 is prepared using the Hummers methods after improving.
Ultrasonic time described in step 2 is 3～10h.
Reaction temperature described in step 5 is 90～150；Reaction time described in DEG C is 1～3 day.
Above-mentioned polystyrene (PS) for the synthetic route of the multilayer functionalization graphene nano-hybrid material of hinge is：
Compared with prior art, if according to conventional synthetic route, from GO, through GO-Cl, GO-CDs to GO-
CDs-PS.Through experimental studies have found that, finally will be unable to obtain any target product.The polystyrene (PS) that the present invention is provided is hinge
System of the one pot of preparation method of the multilayer functionalization graphene nano-hybrid material of chain in functionalization graphene nano-hybrid material
During standby, CDs and PS introduced by organic covalent modification and Supramolecular self assembly non-covalent modification science scientifically, and is led to
The routine operations such as simple heating stirring, filtration are crossed, prepared by the hydrophobic cavity self assembly for the carboxylic group and CDs on GO surfaces
Form.Also, prepared by one kettle way in the building-up process of the present invention and save a lot of human and material resources and financial resources, and from basic
On protect environment, and be conducive to mass producing.Many layer functions of the polystyrene (PS) that simultaneously prepared by the present invention for hinge
Graphite alkene nano-hybrid material can easily by adjusting reaction temperature, and ratio control CD, PS of reaction mass exist
Load capacity on GO, and then adjust the thermal stability of hybrid material.The introducing of CDs, PS is effectively improved the thermally-stabilised of GO
Performance, while the interface compatibility between polymeric matrix is improve, the phase of compound of birdsing of the same feather flock together especially for improve for property and PS
Patibhaga-nimitta capacitive so as to advantageously build in the thermal stability for improving polymer composites as Nano filling novel fire-retardant
Property nano composite material.In addition, polystyrene is a kind of quite varied polymer of application, light industry, electrically etc. is can be widely used for
Field is used as insulating materials, heat-insulating heat-preserving material, transparent membrane, capacitor dielectric layer etc..But also existence is crisp and heat-resisting simultaneously
The low significant drawback of property.The present invention will greatly increase the compatibility of the grapheme material and PS by PS as hinge.Therefore, originally
Invention can make the hybrid material prepare the nano composite material of PS and its similar polymer for base as Nano filling, in composite wood
Material field has potential using value；It is particularly suitable for use as Nano filling and prepares the nano combined material of heat resistant type flame-retardant polymer
Material.The preparation method of the present invention presses close to the requirement of Green Chemistry, and simple to operate, it is easy to controls, is conducive to industrial mass
Production.
Below in conjunction with the accompanying drawings embodiments of the invention are described in further detail.
Description of the drawings
Fig. 1 is the multilayer functionalization graphene nano-hybrid material preparation process that polystyrene prepared by the present invention is hinge
Schematic diagram.
Fig. 2 is the multilayer functionalization graphene nano hybridization that the polystyrene synthesized in the embodiment of the present invention 1 and 2 is hinge
The infrared spectrogram of material.
Fig. 3 is the embodiment of the present invention 1, multilayer functionalization graphene nano hybridization of the polystyrene synthesized in 2 for hinge
The thermally-stabilised analysis curve of material.
Specific embodiment
Below in conjunction with the accompanying drawings embodiments of the invention are described in further detail, the present embodiment is with the technology of the present invention side
Implemented under the premise of case, given detailed embodiment and specific operating process, but protection scope of the present invention is not limited
In following embodiments.
As shown in figure 1, a kind of polystyrene (PS) multilayer functionalization graphene nano-hybrid material and one for hinge
Pot preparation method, the method are comprised the following steps：
Step 1, with natural flake graphite powder using improve after Hummers methods prepare prepare oxidation graphite solid；
The lower 3-10h of step 2, ultrasound, the ratio for preparing graphene oxide DMF suspension, graphite oxide and DMF solvent is 7.5
～15mg/mL；
Step 3, by add in graphene oxide DMF suspension excessive thionyl chloride react at 70-90 DEG C to
After few one day, vacuum distillation is removing unnecessary SOCl2After obtain, the ratio of wherein described graphite oxide and thionyl chloride is little
In 10mg/mL (GOCl)；
Step 4, the DMF solution for preparing CDs and PS, the mass ratio of CD and PS is (50：1)～(1：50)；CDs and DMF's
Than for 0.67～120mg/mL；
Step 5, the GOCl for obtaining step 3 are mixed with the CDs and the DMF solution of PS that prepare in step 4, it is heated to 90～
150 DEG C of stirring reactions 1～3 day, wherein, graphene oxide is (30 with the mass ratio of CDs：1)～(1：30)；
Step 6, filtration under diminished pressure, washing, obtain functionalization graphene nano-hybrid material after drying.
Embodiment 1
The first step, the preparation of oxidation graphite solid；
At 80 DEG C, 20g native graphites (400 mesh) is pre- with the 30mL concentrated sulfuric acids, 10g potassium peroxydisulfates and 10g phosphorus pentoxides
After oxidation, pH=7 is washed to, air drying is overnight stand-by；
The 460mL concentrated sulfuric acids are cooled to 0 DEG C or so, then the graphite that 20g is pre-oxidized are added thereto, are slowly added into
60g potassium permanganate so that system temperature to add and be warmed up to 35 DEG C after finishing less than 20 DEG C, after stirring 2h, and in batches slowly
Add 920mL deionized waters so that system temperature is less than 98 DEG C, after being stirred for 15 minutes, add 2.8L deionized waters and
50mL30% hydrogen peroxide.By the glassy yellow suspension for obtaining decompression suction filtration, washing.Until without sulfate ion in filtrate,
And during in neutrality, product is dried in 60 DEG C of vacuum, oxidation graphite solid is obtained；
200mg graphite oxides powder is loaded round-bottomed flask, adds 15mL DMFs by second step
(DMF) solvent, after ultrasonic 7h, obtains the suspension of graphene oxide；
3rd step, adds 40mL thionyl chloride (SOCl in the suspension in second step2), after reacting 24h at 70 DEG C,
Vacuum distillation is removing unnecessary SOCl2Obtain the product (GO-Cl) of activated carboxylic.
4th step, weighs 4g beta-schardinger dextrins (β-CDs) and 0.2g PS are added in 42mL DMF and stir to being completely dissolved,
Prepare the DMF solution of CDs/PS；
5th step, the DMF solution of the CDs/PS that the 4th step is obtained are added in the GOCl reaction bulbs of the 3rd step, adjust temperature
Spend to 100 DEG C, constant temperature stirring reaction 2 days；
6th step, the crude product that the 5th step is obtained are washed through suction filtration, after drying, obtain final product product.
Infrared spectrum is as shown in Figure 2 e, it was demonstrated that the nano-hybrid material successfully synthesizes.
As shown in Figure 3 c, in figure, the thermal stability of functionalization graphene nano-hybrid material is not higher than for its heat endurance
The graphene oxide of modification, and intermediate product.
Embodiment 2
First to the 3rd step, with step one in embodiment 1 to three.
4th step, weighs 0.2g alpha-cyclodextrins (β-CDs) and 0.2g PS are added in 30mL DMF and stir to completely molten
Solution, prepares the DMF solution of CDs/PS；
5th to the 6th step, with step 5 in embodiment 1 to six.
Infrared spectrum is as shown in figure 2f, it was demonstrated that the nano-hybrid material successfully synthesizes.
As shown in Figure 3 a, in figure, the thermal stability of functionalization graphene nano-hybrid material is not higher than for its heat endurance
The graphene oxide of modification, and intermediate product.
Embodiment 3
First to the 3rd step, with step one in embodiment 1 to three.
4th step, weighs 6g beta-schardinger dextrins (β-CDs) and 0.2g PS are added in 50mL DMF and stir to being completely dissolved,
Prepare the DMF solution of CDs/PS；
5th to the 6th step, with step 5 in embodiment 1 to six.
Embodiment 4
First to the 3rd step, with step one in embodiment 1 to three.
4th step, weighs 40mg beta-schardinger dextrins (β-CDs) and 2g PS are added in 10mL DMF and stir to being completely dissolved,
Prepare the DMF solution of CDs/PS；
5th to the 6th step, with step 5 in embodiment 1 to six.
Embodiment 5
First to the 3rd step, with step one in embodiment 1 to three.
4th step, weighs 100mg beta-schardinger dextrins (β-CDs) and 1g PS are added in 30mL DMF and stir to being completely dissolved,
Prepare the DMF solution of CDs/PS；
5th to the 6th step, with step 5 in embodiment 1 to six.
Embodiment 6
First to the 3rd step, with step one in embodiment 1 to three.
4th step, weighs 0.2g alpha-cyclodextrins (β-CDs) and 0.3g PS are added in 15mL DMF and stir to completely molten
Solution, prepares the DMF solution of CDs/PS；
5th to the 6th step, with step 5 in embodiment 1 to six.
Embodiment 7
First to fourth step, with step one in embodiment 1 to four.
5th step, the DMF solution of the CDs/PS that the 4th step is obtained are added in the GOCl reaction bulbs of the 3rd step, adjust temperature
Spend to 90 DEG C, constant temperature stirring reaction 3 days；
6th step, with step 6 in embodiment 1.
Embodiment 8
First to fourth step, with step one in embodiment 7 to four.
5th step, the DMF solution of the CDs/PS that the 4th step is obtained are added in the GOCl reaction bulbs of the 3rd step, adjust temperature
Spend to 150 DEG C, constant temperature stirring reaction 1 day；
6th step, with step 6 in embodiment 1.
Embodiment 9
First to fourth step, with step one in embodiment 2 to four.
5th step, the DMF solution of the CDs/PS that the 4th step is obtained are added in the GOCl reaction bulbs of the 3rd step, adjust temperature
Spend to 120 DEG C, constant temperature stirring reaction 2 days；
6th step, with step 6 in embodiment 1.
Embodiment 10
First to the 3rd step, with step one in embodiment 1 to three.
4th step, weighs 6.7mg alpha-cyclodextrins (β-CDs) and 0.03g PS are added in 10mL DMF and stir to completely molten
Solution, prepares the DMF solution of CDs/PS；
5th to the 6th step, with step 5 in embodiment 1 to six.
Embodiment 11
First to the 3rd step, with step one in embodiment 1 to three.
4th step, weighs 6g beta-schardinger dextrins (β-CDs) and 10g PS are added in 100mL DMF and stir to being completely dissolved,
Prepare the DMF solution of CDs/PS；
5th to the 6th step, with step 5 in embodiment 1 to six.
Embodiment 12
The first step, with step one in embodiment 1.
200mg graphite oxides powder is loaded round-bottomed flask, adds 15mL DMFs by second step
(DMF) solvent, after ultrasonic 10h, obtains the suspension of graphene oxide；
3rd to the 6th step, with step 3 in embodiment 1 to six.
Embodiment 13
The first step, with step one in embodiment 2.
200mg graphite oxides powder is loaded round-bottomed flask, adds 15mL DMFs by second step
(DMF) solvent, after ultrasonic 3h, obtains the suspension of graphene oxide；
3rd to the 6th step, with step 3 in embodiment 2 to six.
Knowable to above-described embodiment, the polystyrene (PS) that the present invention is provided is the multilayer functionalization graphene nanometer of hinge
Hybrid material and one pot preparation method dexterously two kinds of classical covalent modification technology in integrated use Synthetic Organic Chemistry,
By one pot reaction simultaneously by CDs, PS is anchored on the edge of GO.This method solve according to conventional synthetic route, go out from GO
Send out, through GO-Cl, GO-CDs to GO-CDs-PS.Through the course that experiment cannot obtain any target product.The present invention is provided
One pot of preparation method saves human and material resources and financial resources, and fundamentally protects environment, is conducive to mass producing.
Claims (5)
1. a kind of polystyrene is the preparation method of the multilayer functionalization graphene nano-hybrid material of hinge, it is characterised in that
The method comprising the steps of：
Step 1, with natural flake graphite powder prepare oxidation graphite solid；
Under step 2, ultrasound, the DMF suspension of graphene oxide, graphite oxide and N, N- dimethyl is prepared
The ratio of formamide solvent is 7.5～15mg/mL；
Step 3, the graphene oxide GOCl for preparing activated carboxylic；
Step 4, the DMF solution for preparing cyclodextrin and polystyrene, wherein, cyclodextrin and polystyrene
Mass ratio is (50：1)～(1：50), the ratio of cyclodextrin and DMF is 0.67～120mg/mL, and cyclodextrin is
Alpha-cyclodextrin or beta-schardinger dextrin；
The cyclodextrin for preparing in step 5, the GOCl that step 3 is obtained and step 4 and the N,N-dimethylformamide of polystyrene
Solution mixes, and heating stirring is reacted, and wherein, graphene oxide is (30 with the mass ratio of cyclodextrin：1)～(1：30)；
Step 6, filtration under diminished pressure, washing, obtain functionalization graphene nano-hybrid material after drying.
2. polystyrene according to claim 1 is the preparation side of the multilayer functionalization graphene nano-hybrid material of hinge
Method, it is characterised in that the ultrasonic time described in step 2 is 3～10h.
3. polystyrene according to claim 1 is the preparation side of the multilayer functionalization graphene nano-hybrid material of hinge
Method, it is characterised in that the GOCl described in step 3 is by adding in the DMF suspension to graphene oxide
Enter after excessive thionyl chloride reacts at least 1 day at 70-90 DEG C, vacuum distillation is obtained after removing unnecessary thionyl chloride, its
Described in graphite oxide and the ratio of thionyl chloride be not more than 10mg/mL.
4. polystyrene according to claim 1 is the preparation side of the multilayer functionalization graphene nano-hybrid material of hinge
Method, it is characterised in that the reaction temperature described in step 5 is 90～150 DEG C；The described stirring reaction time is 1～3 day.
5. the polystyrene for being prepared according to the arbitrary described preparation method of claim 1-4 is the multilayer functionalization graphene of hinge
Nano-hybrid material.
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| KR20110069201A (en) * | 2009-12-17 | 2011-06-23 | 거림테크 주식회사 | Dispertion method of carbon nano sheet |
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