CN104497232B - Preparation of controllable monodisperse polystyrene microsphere grafted graphene and product thereby - Google Patents
Preparation of controllable monodisperse polystyrene microsphere grafted graphene and product thereby Download PDFInfo
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Abstract
The invention discloses a preparation method of controllable monodisperse polystyrene microsphere grafted graphene. The method comprises the following steps: (1) pretreatment of polystyrene; (2) water-removing treatment of methylbenzene; (3) preparation of graphene oxide; (4) preparation of acryloyl chloride; (5) preparation of graphene oxide grafted acryloyl chloride; and (6) preparation of graphene oxide surface grafted with polystyrene microspheres. According to the method disclosed by the invention, the advantages of the graphene oxide and polystyrene can be put into a full play by grafting the polystyrene microspheres on the graphene oxide; the dispersity and the molding processability of the graphene oxide in a substrate are improved; and the micro-structure of a composite material is optimized. The particle sizes of the polystyrene (PS) microspheres can be indirectly controlled through control over the amount of a dispersant sodium dodecyl benzene sulfonate (SDS); the controllability of the particle sizes of the polymer microspheres is achieved; the composite material obtained by grafting the polymer microspheres on the graphene oxide surface can be applied to the fields such as standard metering, medical immunology, bioengineering, analytical chemistry, chemical industry and microelectronics.
Description
Technical field
The invention belongs to new material technology field, it is related to a kind of system of controlled monodisperse polystyrene microsphere graft grapheme
Standby and products thereof.
Background technology
Graphene oxide is the oxide of Graphene, has monoatomic layer structure, close to plane and assume two-dimension netted knot
Structure, specific surface area is big, and substantial amounts of oxygen-content active functional group is contained on surface, such as the hydrophilic base such as hydroxyl, carboxyl, carbonyl, epoxy radicals
Group, has good stability and biocompatibility, is a kind of new carbon of excellent performance.Be commonly applied to biologic medical,
The field such as sensor and composite.
The eighties in 20th century, Vanderhoff et al. once used seed emulsion polymerization under spaceborne below-G conditions
It is made for the Monodisperse Polystyrene Microspheres that particle diameter is 2～30 μm.Polymer microballoon has that specific surface is big, adsorptivity strong, agglutination
Big and have the specific physiques such as surface respond, it is commonly applied to standard metering, medical immunology, biological engineering, analytical chemistry, change
Learn the fields such as industry and microelectronics.
The preparation method of graphene oxide mainly has：Brodie method, Hummers method and Staudenmaier method,
First process graphite with strong protonic acid so as to form compound between graphite layers, adding strong oxidizer, compound between graphite layers are entered
Row oxidation.Wherein Hummers method is to prepare the effective ways of graphene oxide in a large number, and the graphene oxide preparing has
Preferably dispersibility.
The method that graphenic surface is modified
Surface physics is modified：Between modifying agent and nanoparticle, no chemical reaction occurs, i.e. no ionic bond or covalently bonded
Close.Modifying agent passes through the effect absorption such as Van der Waals force, hydrogen bond or coordinate bond on the surface of nanoparticle.
Surface chemical modification：Chemical reaction between nanoparticle and modifying agent, introduces modifying agent in nanoparticle surface,
Thus changing nanoparticle surface structure and state, reach the purpose of modification.
The present invention utilizes the oxy radical of surface of graphene oxide and acryloyl chloride to react formation reactivity site, will have
The polystyrene microsphere of active end moieties acts on " being grafted to " (Grafting to) graphene oxide table by chemical bonding
Face active site forms polystyrene microsphere graft grapheme, and reaction can be carried out in the solution or under molten condition.To graphite oxide
Alkene is chemically modified and functionalization, thus improving its performance, adjusts its physicochemical properties.
Content of the invention
It is an object of the invention to provide a kind of preparation method of controlled monodisperse polystyrene microsphere graft grapheme and product
Product.
The technical solution used in the present invention：A kind of preparation method of controlled monodisperse polystyrene microsphere graft grapheme,
Comprise the steps of：
（1）Cinnamic pretreatment：Styrene monomer with 5% sodium hydroxide cyclic washing, then be washed with deionized to
PH close to 7, then eliminating water 12 h, finally by styrene vacuum distillation；
（2）Toluene removes water process：The metallic sodium being of moderate size and benzophenone is added, heating makes solution protect in toluene solution
Hold boiling until solution colour becomes navy blue, air-distillation can get dry toluene；
（3）The preparation of graphene oxide：Dried crystalline flake graphite is added to equipped with potassium nitrate and concentrated sulphuric acid mixture
Container in, ultrasonic mixing uniformly, stirs in ice-water bath and is slowly added to potassium permanganate；System temperature T therewith1Rise to 30 DEG C,
High-speed stirred reacts 6 h；It is slowly added to distilled water, system temperature T therewith2It is warming up to 60 DEG C and react 0.5 h；Again in system
(mass percentage concentration is 30% to add distilled water and hydrogen peroxide）, obtain graphene oxide mother solution, distilled water centrifuge washing, obtain
Pure graphene oxide, adds appropriate dodecylbenzene sodium sulfonate wherein, and ultrasonic mixing uniformly, that is, obtains graphite oxide
Alkene gel；
（4）The preparation of acryloyl chloride：Thionyl chloride and acrylic acid react 12 h in ice-water bath；
（5）The preparation of graphene oxide grafted propylene acyl chlorides：Graphene oxide and acryloyl chloride dissolve in dry toluene, put
Enter in container, then ultrasonic mixing uniformly, places in 50 DEG C of oil baths and reacts 24 h, the black product obtaining toluene repeatedly from
The heart washs, then with ethanol rinse, is dried；
（6）The preparation of surface of graphene oxide grafted polystyrene microsphere：The graphene oxide dissolving of grafted propylene acyl chlorides
To in the container equipped with deionized water；SDS is soluble in water, add styrene monomer, ultrasonic mixing uniformly, is added to container
In, by the constant temperature oil bath of 65 DEG C of container under nitrogen protection, it is stirred at reflux reaction 30 min；By potassium peroxydisulfate（KPS）It is soluble in water,
It is added to after mix homogeneously in container, reacts 3 h, reactant mixture uses ethanol, distilled water wash respectively, be dried, aoxidized
The composite of graphenic surface grafted polystyrene microsphere.
Step（3）Middle crystalline flake graphite alkene is 1 g with the mass ratio of potassium nitrate:（1.0～1.6 g）, crystalline flake graphite alkene with dense
The amount ratio of sulphuric acid is 1.0 g:（30～60 mL）, reaction temperature T1For（30～45 DEG C）,
Reaction temperature T2For（60～75 DEG C）.
A kind of controlled monodisperse polystyrene microsphere graft grapheme of the preparation method preparation described in basis.
On graphene oxide of the present invention, to give full play to Graphene respective with polystyrene excellent for grafted polystyrene microsphere
Point, improves graphene oxide dispersibility in the base and molding processibility, optimizes the micro structure of composite.By to point
Powder dodecylbenzene sodium sulfonate（SDS）The control of amount is indirectly controlled microsphere polystyrene（PS）The particle diameter of microsphere, realizes poly-
Compound microspherulite diameter Modulatory character.
The invention has the advantages that：
（1）On graphene oxide grafted polystyrene microsphere formed polymer microballoon have larger specific surface area,
Even particle size distribution.
（2）Prepared polystyrene microsphere graft grapheme can be stable be dispersed in water and organic solvent toluene,
In chloroform, low cost, workable.
（3）Indirectly control the size of microspherulite diameter by controlling SDS amount, realize the Modulatory character of microspherulite diameter.
（4）Product surface of graphene oxide being modified obtain can operate with the composite woods such as biologic medical, sensor
Material.
Brief description
Fig. 1 is the infrared spectrogram of graphene oxide grafted propylene acyl chlorides.
Fig. 2 is grafted infrared spectrogram for polystyrene microsphere graft grapheme.
Fig. 3 is graphene oxide（a、b）With Graphene in water deliquescent photo.
Fig. 4 is graphene oxide（a、b）, polystyrene microsphere graft grapheme（c、d）, graphite oxide and polystyrene micro-
Ball mixture（e、f）Deliquescent photo in toluene and chloroform.
Fig. 5 is that the field emission scanning electron microscope of the polystyrene microsphere graft grapheme of preparation under adding different SDS amounts shines
Piece.
Specific embodiment
Embodiment 1：
A kind of preparation method of controlled monodisperse polystyrene microsphere graft grapheme, follows the steps below：
（1）Cinnamic pretreatment：Styrene monomer is washed with 5% sodium hydroxide cyclic washing, then is washed with deionized
To PH close to 7, it is then placed in eliminating water 12 h in molecular sieve, finally styrene is put into vacuum distillation in Rotary Evaporators.
（2）Toluene removes water process：The metallic sodium being of moderate size and 0.3 g benzophenone is added, heating makes in toluene solution
Solution keeps boiling until solution colour becomes navy blue, and air-distillation can get dry toluene.
（3）The preparation of graphene oxide：Dried crystalline flake graphite 1.0 g is added to equipped with potassium nitrate 1.0 g and dense
In 250 mL four-hole boiling flasks of sulphuric acid 30 mL mixture, ultrasonic 30 min mix homogeneously, stir in ice-water bath and are slowly added to height
Potassium manganate 6.0 g.System temperature T therewith1Rise to 30 DEG C, high-speed stirred reacts 6 h.It is slowly added to distilled water 80 mL, body therewith
It is temperature T2It is warming up to 60 DEG C and react half an hour.(percent mass is dense to add distilled water 100 mL and hydrogen peroxide again in system
Spend for 30%）6 mL simultaneously react 5 min, obtain jonquilleous graphene oxide mother solution.Distilled water centrifuge washing, to pH=6, obtains
Pure graphene oxide, adds appropriate dodecylbenzene sodium sulfonate, ultrasonic 30 min mix homogeneously wherein, that is, obtains oxygen
Graphite alkene gel.
（4）The preparation of acryloyl chloride：1.0 g thionyl chlorides and 1.0 g acrylic acid react 12 h in ice bath.
（5）The preparation of graphene oxide grafted propylene acyl chlorides：0.06 g graphene oxide and 10 mL acryloyl chlorides dissolve in 16
In mL dry toluene, put in 50 mL round-bottomed flasks, then ultrasonic 20 min, place in 50 DEG C of oil baths and react 24 h.Obtain
Black product toluene be centrifuged repeatedly washing, then use ethanol rinse.It is finally putting in drying baker and be dried.Using fourier infrared
Spectrogrph（FTIR）The structure of the graphene oxide of grafting acryloyl chloride is characterized, such as Fig. 1.
（6）The preparation of surface of graphene oxide grafted polystyrene microsphere：The graphite oxide of 0.05 g grafted propylene acyl chlorides
Alkene is dissolved in the round-bottomed flask equipped with 40 mL deionized waters；0.0276 gSDS is dissolved in 15 mL water, adds 1.8 g benzene
Vinyl monomer, ultrasonic 30 min mix homogeneously, it is added in round-bottomed flask, under nitrogen protection, round-bottomed flask is put into 65 DEG C of perseverance
In warm oil bath pan, it is stirred at reflux reaction 30 min；By 0.06 g initiator potassium persulfate（KPS）It is dissolved in 15 ml water, mixing
It is added in round-bottomed flask after uniformly, react 3 h.Reactant mixture uses ethanol, distilled water wash respectively, dry in 40 DEG C of baking ovens
Dry.Using Fourier infrared spectrograph（FTIR）, field emission scanning electron microscope（SEM）The structure and shape characteristic of target product is entered
Row characterizes, result such as Fig. 2 and Fig. 5（a）.
Embodiment 2：
Step（3）Middle crystalline flake graphite alkene 1.0 g, potassium nitrate 1.2 g, concentrated sulphuric acid 40 mL；Reaction temperature T1 is 35 DEG C, instead
Temperature T2 is answered to be 65 DEG C；Distilled water centrifuge washing pH=7；
Step（4）In acrylic acid quality used be 1.1 g；
Step（5）In acryloyl chloride used and dry toluene volume be respectively 12 mL and 18 mL；
Step（6）In the quality of dispersion stabilizer SDS used be 0.0552 g, the quality of initiator KPS is 0.08 g
, the quality of monomer styrene is 2.0 g, and the volume of decentralized medium water is 60 mL, and reaction temperature is 70 DEG C,
Other identical with specific embodiment 1.
Using field emission scanning electron microscope（SEM）The structure and shape characteristic of target product is characterized, result such as Fig. 5
（b）.
Embodiment 3：
Step（3）Middle crystalline flake graphite alkene 1.0 g, potassium nitrate 1.4 g, concentrated sulphuric acid 50 mL；Reaction temperature T1 is 40 DEG C, instead
Temperature T2 is answered to be 70 DEG C；Distilled water centrifuge washing pH=8；
Step（4）In acrylic acid quality used be 1.2 g；
Step（5）In acryloyl chloride used and dry toluene volume be respectively 14 mL and 20 mL；
Step（6）In the quality of dispersion stabilizer SDS used be 0.0828 g, the quality of initiator KPS is 0.10g,
The quality of monomer styrene is 2.2 g, and the volume of decentralized medium water is 80 mL, and reaction temperature is 75 DEG C,
Other identical with specific embodiment 1.
Using field emission scanning electron microscope（SEM）The structure and shape characteristic of target product is characterized, result such as Fig. 5
（c）.
Embodiment 4：
Step（3）Middle crystalline flake graphite alkene 1.0 g, potassium nitrate 1.6 g, concentrated sulphuric acid 60 mL；Reaction temperature T1 is 45 DEG C, instead
Temperature T2 is answered to be 75 DEG C；Distilled water centrifuge washing pH=9；
Step（4）In acrylic acid quality used be 1.3 g；
Step（5）In acryloyl chloride used and dry toluene volume be respectively 16 mL and 22 mL；
Step（6）In the quality of dispersion stabilizer SDS used be 0.1104 g, the quality of initiator KPS is 0.12g,
The quality of monomer styrene is 2.4 g, and the volume of decentralized medium water is 100 mL, and reaction temperature is 80 DEG C,
Other identical with specific embodiment 1.
Using field emission scanning electron microscope（SEM）The structure and shape characteristic of target product is characterized, result such as Fig. 5
（d）.
Performance test is carried out to the controlled monodisperse polystyrene microsphere graft grapheme of gained of the present invention, result is as follows:
1st, graphene oxide and the contrast test result deliquescent in water of Graphene show：Graphene oxide is in water
Dispersibility very well, dispersibility in water for the Graphene is poor.Fig. 3 is that the dissolving in water of graphene oxide and Graphene is shone
Piece.
2nd, graphene oxide, polystyrene microsphere graft grapheme, graphite oxide and polystyrene microsphere mixture are in first
In benzene and chloroform, deliquescent contrast test result shows：Polystyrene microsphere graft grapheme is nano combined within a certain period of time
Material can stably be present in (c.d in Fig. 4) in toluene and chloroformic solution, and graphene oxide is dispersed in toluene and chlorine respectively
Start in imitative that precipitation occurs after supersound process at once（A.b in Fig. 4）, graphene oxide and polystyrene microsphere mixed
Compound is dispersed among toluene and chloroform respectively（E.f in Fig. 4）.
Claims (3)
1. a kind of preparation method of controlled monodisperse polystyrene microsphere graft grapheme is it is characterised in that comprise the steps of：
（1）Cinnamic pretreatment：Styrene monomer, with 5% sodium hydroxide cyclic washing, then is washed with deionized and connects to pH
Nearly 7, then eliminating water 12 h, finally by styrene vacuum distillation；
（2）Toluene removes water process：The metallic sodium being of moderate size and benzophenone is added, heating makes solution keep boiling in toluene solution
Rise until solution colour becomes navy blue, air-distillation can get dry toluene；
（3）The preparation of graphene oxide：Dried crystalline flake graphite is added to the appearance equipped with potassium nitrate and concentrated sulphuric acid mixture
In device, ultrasonic mixing uniformly, stirs in ice-water bath and is slowly added to potassium permanganate；System temperature T therewith1Rise to 30 DEG C, at a high speed
Stirring reaction 6 h；It is slowly added to distilled water, system temperature T therewith2It is warming up to 60 DEG C and react 0.5 h；Add in system again
Distilled water and the hydrogen peroxide that mass percentage concentration is 30%, obtain graphite oxide mother solution, distilled water centrifuge washing, obtain pure
Graphite oxide, adds appropriate dodecylbenzene sodium sulfonate wherein, and ultrasonic mixing uniformly, that is, obtains graphene oxide gel；
（4）The preparation of acryloyl chloride：Thionyl chloride and acrylic acid react 12 h in ice-water bath；
（5）The preparation of graphene oxide grafted propylene acyl chlorides：Graphene oxide and acryloyl chloride dissolve in dry toluene, put into appearance
In device, then ultrasonic mixing uniformly, places in 50 DEG C of oil baths and reacts 24 h, the black product toluene obtaining is centrifuged repeatedly to be washed
Wash, then with ethanol rinse, be dried；
（6）The preparation of surface of graphene oxide grafted polystyrene microsphere：The graphene oxide of grafted propylene acyl chlorides is dissolved into dress
Have in the container of deionized water；SDS is soluble in water, add styrene monomer, ultrasonic mixing uniformly, is added in container, nitrogen
Under gas shielded, container is put in 65 DEG C of constant temperature oil bath, be stirred at reflux reaction 30 min；By potassium peroxydisulfate（KPS）It is dissolved in water
In, it is added to after mix homogeneously in container, reacts 3 h, reactant mixture uses ethanol, distilled water wash respectively, be dried, gathered
Phenylethylene micro ball graft grapheme.
2. the preparation method of controlled monodisperse polystyrene microsphere graft grapheme according to claim 1, its feature exists
In step（3）Middle crystalline flake graphite is 1 g with the mass ratio of potassium nitrate:（1.0～1.6 g）, the consumption of crystalline flake graphite and concentrated sulphuric acid
Than for 1.0 g:（30～60 mL）.
3. a kind of controlled monodisperse polystyrene microsphere graft grapheme of preparation method preparation according to claim 1.
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| CN106477559B (en) * | 2015-08-26 | 2018-11-09 | 深圳市润麒麟科技发展有限公司 | A kind of graphene and preparation method thereof |
| CN105199436A (en) * | 2015-10-28 | 2015-12-30 | 沈阳化工大学 | Preparation method for copolymerization living polymer modified graphene oxide |
| CN105891483B (en) * | 2016-04-06 | 2017-11-14 | 扬州大学 | A kind of preparation method of the unmarked electrochemical immunosensor based on graphene parcel polystyrene composite Nano ball |
| CN105949395B (en) * | 2016-05-24 | 2018-02-27 | 华南理工大学 | A kind of molecule clustered materials of supermolecule polymer and its preparation method and application |
| CN106893181A (en) * | 2017-03-16 | 2017-06-27 | 于秀艳 | Graphene of chemical bonding polyethylene long-chain and preparation method thereof |
| CN113527819B (en) * | 2021-08-13 | 2022-07-29 | 河北科技大学 | Reduced graphene oxide polystyrene composite material and preparation method thereof |
| CN114437467B (en) * | 2022-03-04 | 2023-05-12 | 深圳石墨烯创新中心有限公司 | Preparation method of graphene oxide-polystyrene composite material |
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| CN102504145A (en) * | 2011-11-15 | 2012-06-20 | 苏州大学 | Preparation method for polymer grafted graphene oxide |
| WO2014034156A1 (en) * | 2012-08-27 | 2014-03-06 | 積水化学工業株式会社 | Flaked graphite resin composite material and method for producing same |
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| CN102504145A (en) * | 2011-11-15 | 2012-06-20 | 苏州大学 | Preparation method for polymer grafted graphene oxide |
| WO2014034156A1 (en) * | 2012-08-27 | 2014-03-06 | 積水化学工業株式会社 | Flaked graphite resin composite material and method for producing same |
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