CN111825860B - Graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere and preparation method thereof - Google Patents

Graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere and preparation method thereof Download PDF

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CN111825860B
CN111825860B CN202010548522.0A CN202010548522A CN111825860B CN 111825860 B CN111825860 B CN 111825860B CN 202010548522 A CN202010548522 A CN 202010548522A CN 111825860 B CN111825860 B CN 111825860B
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graphene
silicon dioxide
microsphere
wall material
polystyrene microsphere
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CN111825860A (en
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李爽
杨波
张双红
李海燕
李悦
郭华超
徐青永
文芳
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Guangzhou Special Pressure Equipment Inspection and Research Institute
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/128—Polymer particles coated by inorganic and non-macromolecular organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention relates to a graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere and a preparation method thereof. The graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere comprises a polystyrene microsphere, and a silicon dioxide layer and a graphene layer which are sequentially coated on the surface of the polystyrene microsphere; the silicon dioxide layer is connected with the graphene layer through a polydopamine layer. The polystyrene microsphere has good thermal stability and mechanical property, the functionality of the polystyrene microsphere is improved by modifying the double-hybrid wall material, and the application range is wide.

Description

Graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere and preparation method thereof
Technical Field
The invention relates to the technical field of polymer microspheres, in particular to a graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere and a preparation method thereof.
Background
The polymer microsphere has the characteristics of large specific surface area, high reaction activity, easy functionalization, strong adsorbability and the like, and can be widely applied to the fields of supercapacitors, catalysis, analytical chemistry, biomedicine and the like. The Polystyrene (PS) microspheres are polymerized from styrene monomers, and have the advantages of good surface reaction capability, corrosion resistance, difficult deformation and the like, but the polystyrene microspheres have the defects of low thermal stability and single function, and limit further application of the polystyrene microspheres.
Aiming at the defect of single function, the traditional solution method is to wrap inorganic nanoparticles on the surface of the PS microsphere to prepare the PS-based core-shell microsphere. The PS-based core-shell microsphere has the advantages of the PS microsphere, and meanwhile, the shell particles can endow the microsphere with functions of light, electricity, magnetism, catalysis and the like, so that the PS-based core-shell microsphere has a better application prospect in the fields of catalysis, biomedicine, materials and the like. To date, there are many physical and chemical methods for synthesizing hybrid microspheres, including layer-by-layer self-assembly, sol-gel reaction, molecular self-assembly, biomimic mineralization, polyamine salt aggregation-assisted assembly, pickering emulsion technology-assisted assembly, and other interfacial polymerization reactions. However, one of the major drawbacks of PS-based core-shell microspheres is that: due to the core-shell structure, the strength of the adhesive force between the shell layer and the PS-based core directly influences the multifunctional exertion of the core layer of the PS-based core-shell microsphere, and the thermal stability and the mechanical property of the microsphere can be further reduced. Meanwhile, due to the existence of the defect, the PS-based core-shell microspheres modified by single inorganic hybrid wall materials which can be prepared at present are mostly limited in the multifunctional development of the PS microspheres, and with the development of industry and the improvement of science and technology, the PS-based core-shell microspheres modified by single inorganic hybrid wall materials cannot meet the requirements of higher load, high temperature and multiple functions.
Disclosure of Invention
Based on the above, there is a need to provide a graphene/silica double hybrid wall material modified polystyrene microsphere. The polystyrene microsphere has good thermal stability and mechanical property, the functionality of the polystyrene microsphere is improved by modifying the double-hybrid wall material, and the application range is wide.
The specific technical scheme is as follows:
a graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere comprises a polystyrene microsphere, and a silicon dioxide layer and a graphene layer which are sequentially coated on the surface of the polystyrene microsphere;
the silicon dioxide layer is connected with the graphene layer through a polydopamine layer.
In one embodiment, the particle size of the graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere is 5-10 micrometers, and the glass transition temperature is 250-280 ℃.
The invention also provides a preparation method of the graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere, which comprises the following steps:
(a) Dispersing oleophylic modified nano silicon dioxide in water, adding a styrene monomer, a cross-linking agent and an initiator into the obtained dispersion liquid, and emulsifying to obtain O/W type emulsion; polymerizing the O/W type emulsion to obtain polystyrene/SiO 2 Microspheres;
(b) Mixing the polystyrene/SiO 2 Dispersing the microspheres in water to obtain a microsphere dispersion liquid; under the neutral or alkaline condition, mixing the microsphere dispersion liquid with dopamine salt, and carrying out polymerization reaction on the obtained mixed solution to obtain intermediate microspheres;
(c) And mixing the intermediate microspheres with the graphene aqueous dispersion, and carrying out grafting reaction.
In one embodiment, in step (a), the crosslinking agent is selected from: at least one of divinylbenzene, N-methylolacrylamide, acrylic acid and hydroxyethyl acrylate.
In one embodiment, in step (a), the initiator is selected from: at least one of azodiisobutyronitrile, benzoyl peroxide, dibenzoyl peroxide and potassium persulfate.
In one embodiment, in step (a), the oleophilic modified nano-silica is a silane coupling agent modified nano-silica, and the particle size of the nano-silica is 10-20 nm.
In one embodiment, the silane coupling agent accounts for 0.5-10% of the mass of the nano silica, and is selected from the following group: at least one of isocyanatopropyltriethoxysilane, KH550, KH560 and KH 570.
In one embodiment, in the step (a), the mass ratio of the styrene monomer, the crosslinking agent and the initiator is 5-10: 0.2:0.1 to 0.5.
In one embodiment, in step (a), the oleophilic modified nano-silica accounts for 0.5 to 2% of the mass of the styrene monomer.
In one embodiment, in step (b), the microsphere dispersion is polystyrene/SiO 2 The mass ratio of the microspheres to the dopamine salt is 10.
In one embodiment, in step (b), the pH range of the neutral or basic conditions is 7 to 9.
In one embodiment, in the step (c), the graphene in the graphene aqueous dispersion liquid accounts for 0.1-2% of the mass of the intermediate microsphere.
Compared with the prior art, the invention has the following beneficial effects:
according to the graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere, the surface of the polystyrene microsphere is coated with a layer structure of two nano particles of silicon dioxide and graphene, the silicon dioxide layer and the graphene layer are connected through the polydopamine layer, the polydopamine layer can simultaneously exert adhesion to two nano materials of silicon dioxide and graphene, so that the connection between the silicon dioxide and the graphene is stable, and the graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere has excellent thermal stability and mechanical property. Meanwhile, graphene/silicon dioxide double-hybrid wall material modification is carried out on the polystyrene microsphere, so that multiple functionalities of polydopamine, graphene and silicon dioxide are endowed to the polystyrene microsphere, and the application range is wide.
Drawings
Fig. 1 is an SEM image of the graphene/silica double hybrid wall material modified polystyrene microsphere of example 1.
Detailed Description
The graphene/silica double-hybrid wall material modified polystyrene microsphere and the preparation method thereof of the present invention are further described in detail with reference to specific embodiments below. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The term "coated on a surface" as used herein may mean that there is no additional intermediate structure directly coated on the surface, or there may be an intermediate structure coated on the surface via the intermediate structure.
The embodiment of the invention provides a graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere, which comprises a polystyrene microsphere, a silicon dioxide layer and a graphene layer, wherein the silicon dioxide layer and the graphene layer are sequentially coated on the surface of the polystyrene microsphere;
the silicon dioxide layer is connected with the graphene layer through a polydopamine layer.
Through the layer structure that has two kinds of nano particles of silica and graphite alkene on the surface cladding of polystyrene microballon, just the silica layer with connect through polydopamine layer between the graphite alkene layer, polydopamine layer can form strong bond with two kinds of nano materials of silica and graphite alkene simultaneously, and the performance is to the adhesion of two kinds of nano materials of silica and graphite alkene, makes the stable and firmly fix on polystyrene microballon's surface of connecting between the two. Therefore, the graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere has excellent thermal stability and mechanical property.
Meanwhile, graphene/silicon dioxide double-hybrid wall material modification is carried out on the polystyrene microsphere, so that multiple functionalities of polydopamine, graphene and silicon dioxide are endowed to the polystyrene microsphere, and the application range is wide. In particular, the graphene has excellent conductivity and flexibility, large surface area and good chemical stability, and can make the modified polystyrene microsphere suitable for the electrochemical field, such as preparation of conductive electrodes, supercapacitors, electrochemical catalysts and the like. The silicon dioxide has the optical performance of resisting ultraviolet rays, can improve the ageing resistance, the strength and the chemical resistance of other materials, and can improve the mechanical property and the wear resistance of the modified polystyrene microspheres.
In one specific embodiment, the particle size of the graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere is 5-10 micrometers, and the glass transition temperature is 250-280 ℃. The graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere is small in particle size and can be used in the field of thin coatings or composite materials.
The embodiment of the invention also provides a preparation method of the graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere, which comprises the following steps:
(a) Dispersing oleophylic modified nano silicon dioxide in water, adding a styrene monomer, a cross-linking agent and an initiator into the obtained dispersion liquid, and emulsifying to obtain O/W type emulsion; polymerizing the O/W type emulsion to obtain polystyrene/SiO 2 Microspheres;
(b) Mixing the polystyrene/SiO 2 Dispersing the microspheres in water to obtain a microsphere dispersion liquid; under the neutral or alkaline condition, mixing the microsphere dispersion liquid with dopamine salt, and carrying out polymerization reaction on the obtained mixed solution to obtain intermediate microspheres;
(c) And mixing the intermediate microspheres with the graphene aqueous dispersion, and carrying out grafting reaction.
According to the preparation method, the silicon dioxide layer is firstly prepared to cover the polystyrene microsphere, then the graphene layer is constructed on the outer side of the silicon dioxide layer by utilizing the cross-linking property of the polydopamine, and the composite microsphere of polystyrene, silicon dioxide, polydopamine and graphene is prepared from the outer side to the inner side. The synthesis method provides a new idea for improving the performance of the polystyrene microsphere.
Specifically, the step (a) adopts a Pickering emulsion polymerization method to carry out polystyrene/SiO 2 And (4) preparing the microspheres.
In one particular embodiment, in step (a), the cross-linking agent is selected from: at least one of divinylbenzene, N-methylolacrylamide, acrylic acid and hydroxyethyl acrylate.
In one particular embodiment, in step (a), the initiator is selected from: at least one of azodiisobutyronitrile, benzoyl peroxide, dibenzoyl peroxide and potassium persulfate.
In one specific embodiment, in the step (a), the oleophilic modified nano-silica is a silane coupling agent modified nano-silica, and the particle size of the nano-silica is 10-20 nm. Further, in a specific embodiment, the silane coupling agent accounts for 0 to 10% of the mass of the nano silica, and is selected from the group consisting of: at least one of isocyanatopropyltriethoxysilane, KH550, KH560 and KH 570.
In one specific embodiment, in the step (a), the mass ratio of the styrene monomer, the crosslinking agent and the initiator is 5-10: 0.2:0.1 to 0.5.
In one specific embodiment, in the step (a), the oleophilic modified nano-silica accounts for 0.5 to 2 percent of the mass of the styrene monomer.
In one specific embodiment, the polymerization reaction is as follows: under the protection of inert gas, the temperature is raised to 65-75 ℃ for polymerization. Further, the polymerization reaction is a radical polymerization reaction.
In one specific embodiment, the emulsification is carried out for 3-7 min at a high speed of 15000-25000 r/min.
Specifically, in the step (b), polydopamine-p-polystyrene/SiO is adopted 2 The microspheres are surface modified.
In one specific embodiment, in step (b), the microsphere dispersion is polystyrene/SiO 2 The mass ratio of the microspheres to the dopamine salt is (10).
In one specific embodiment, in step (b), the concentration of dopamine salt in the mixture is not less than 2mg/mL.
In one specific embodiment, in step (b), the pH of the neutral or basic conditions is in the range of 7 to 9. More specifically, the neutral or alkaline conditions are controlled by a buffer, which is Tris buffer.
In one specific embodiment, in step (b), the polymerization conditions are stirring under the neutral or alkaline conditions. So that the dopamine is oxidized and self-polymerized to generate polydopamine which is loaded on the surface of the silicon dioxide/polystyrene microsphere. Specifically, the stirring reaction time is 20-25 h.
In one specific embodiment, in step (b), the dopamine salt is dopamine hydrochloride.
In one specific embodiment, in the step (b), the intermediate microspheres are obtained by: and after the polymerization reaction is finished, centrifuging the mixed system, and removing a supernatant. Further, the resulting intermediate microspheres may be dispersed in water for use.
Specifically, in the step (c), graphene is coated on the basis of the intermediate microsphere by utilizing the cross-linking characteristic of polydopamine, so that the graphene/silicon dioxide double-hybrid wall material polystyrene microsphere is prepared.
In one specific embodiment, in the step (c), graphene in the graphene aqueous dispersion accounts for 0.1-2% of the mass of the intermediate microsphere.
In one specific embodiment, in the step (c), the grafting reaction is performed under stirring at normal temperature. Therefore, the graphene can be grafted to the surface of the microsphere by utilizing the adhesion of polydopamine and the grafting reaction of polydopamine hydroxyl and amino on graphene, so that the graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere is prepared.
The following specific examples are provided, and the raw materials used in the examples are all commercially available unless otherwise specified.
The graphene is purchased from Chengdu organic chemistry GmbH of Chinese academy of sciences, and is aminated graphene, the number of layers is less than 10, and the amino content is 0.5%.
In the following examples, the preparation method of the oleophilic modified nano-silica used is as follows:
dissolving a certain amount of nano silicon dioxide (the particle diameter is 10-20 nm) in an ethanol/water solution with the volume ratio of 3:1, performing ultrasonic dispersion for 10 minutes, and then adding a modifier (isocyano propyl triethoxysilane, which accounts for 5% of the mass of the nano silicon dioxide). And adding the prepared mixed solution into a three-necked bottle, and refluxing for 24 hours at 65 ℃ to obtain the modified silicon dioxide. And (3) carrying out suction filtration on the product, washing the product for 3 times by using ethanol, and drying the product to obtain the oleophylic modified silicon dioxide.
Example 1
The embodiment provides a graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere, and a preparation method thereof comprises the following steps:
(1) Preparation of O/W type Pickering emulsion: adding 0.5g of oleophylic modified nano silicon dioxide into deionized water, and performing ultrasonic dispersion to form uniformly dispersed SiO 2 An aqueous dispersion was prepared by adding 7g of a styrene monomer, 0.2g of divinylbenzene, and 0.276g of azobisisobutyronitrile to SiO 2 Emulsifying in water dispersion at high speed for 5 min with 20000r/min high speed emulsifier to obtain O/W type Pickering emulsion, transferring the obtained O/W type Pickering emulsion into three-neck flask, and adding N 2 Protecting for half an hour, heating to 70 deg.C, free radical polymerizing monomer styrene and divinylbenzene (cross-linking agent) in emulsion under the initiation of azodiisobutyronitrile to form polystyrene/SiO 2 And (3) microspheres.
(2) Dopamine modified polystyrene/SiO 2 Microsphere preparation: 2g of polystyrene/SiO 2 Washing and dispersing the microspheres in 100mL of pure water, adjusting pH to 8.5, adding 0.024g of Tris (hydroxymethyl) aminomethane (Tris), ultrasonically dispersing uniformly while stirring, transferring the mixture into a three-necked bottle, and mixing with the solutionThen 0.2g of dopamine hydrochloride is added dropwise for reaction for 24 hours, after the reaction is finished, the obtained particles are centrifuged to remove unreacted reactants in the supernatant, and finally the particles are dispersed in water for later use.
(3) Preparing the graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere: 2g of dopamine modified polystyrene/SiO obtained in step (2) 2 The microspheres are mixed with 0.2g of graphene aqueous solution (wherein the mass percentage of graphene is 5%), and the mixture is reacted under stirring to obtain the polystyrene microspheres with graphene/polydopamine/silicon dioxide from inside to outside.
Example 2
The embodiment provides a graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere, and a preparation method thereof comprises the following steps:
(1) Preparation of O/W type Pickering emulsion: adding 0.5g of oleophylic modified nano-silica into deionized water, and performing ultrasonic dispersion to form uniformly dispersed SiO 2 An aqueous dispersion was prepared by adding 7g of a styrene monomer, 0.2g of divinylbenzene, and 0.276g of azobisisobutyronitrile to SiO 2 Emulsifying in water dispersion at high speed for 5 min with 20000r/min high speed emulsifier to obtain O/W type Pickering emulsion, transferring the obtained O/W type Pickering emulsion into three-neck flask, and adding N 2 Protecting for half an hour, heating to 70 deg.C, free radical polymerizing monomer styrene and divinylbenzene (cross-linking agent) in emulsion under the initiation of azodiisobutyronitrile to form polystyrene/SiO 2 And (3) microspheres.
(2) Dopamine modified polystyrene/SiO 2 Microsphere: 2g of polystyrene/SiO 2 Washing and dispersing the microspheres in 100mL of pure water, adjusting the pH value to 8.5, then adding 0.024g of Tris (hydroxymethyl) aminomethane (Tris), ultrasonically dispersing uniformly and stirring, transferring the mixed solution into a three-neck bottle, then dropwise adding 0.2g of dopamine hydrochloride for reacting for 24 hours, centrifuging the obtained particles after the reaction is finished, removing unreacted reactants in the supernatant, and finally dispersing in water for later use.
(3) Preparing the graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere: 2g of dopamine modified polystyrene/SiO obtained in step (2) 2 Microspheres and 0.2g stoneMixing graphene aqueous solution (wherein the mass percentage of graphene is 10%), and reacting under stirring to obtain the polystyrene microsphere with graphene/polydopamine/silicon dioxide from inside to outside.
Example 3
The embodiment provides a graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere, and a preparation method thereof comprises the following steps:
(1) Preparation of O/W type Pickering emulsion: adding 0.5g of oleophylic modified nano silicon dioxide into deionized water, and performing ultrasonic dispersion to form uniformly dispersed SiO 2 An aqueous dispersion was prepared by adding 7g of a styrene monomer, 0.2g of divinylbenzene, and 0.276g of azobisisobutyronitrile to SiO 2 Emulsifying in water dispersion at high speed for 5 min with 20000r/min high speed emulsifier to obtain O/W type Pickering emulsion, transferring the obtained O/W type Pickering emulsion into three-neck flask, and adding N 2 Protecting for half an hour, heating to 70 deg.C, free radical polymerizing monomer styrene and divinylbenzene (cross-linking agent) in emulsion under the initiation of azodiisobutyronitrile to form polystyrene/SiO 2 And (3) microspheres.
(2) Dopamine modified polystyrene/SiO 2 Microsphere preparation: 2g of polystyrene/SiO 2 Washing and dispersing the microspheres in 100mL of pure water, adjusting the pH value to 8.5, then adding 0.024g of Tris (hydroxymethyl) aminomethane (Tris), ultrasonically dispersing uniformly and stirring, transferring the mixed solution into a three-neck bottle, then dropwise adding 0.15g of dopamine hydrochloride for reacting for 24 hours, centrifuging the obtained particles after the reaction is finished, removing unreacted reactants in the supernatant, and finally dispersing in water for later use.
(3) Preparing the graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere: 2g of dopamine modified polystyrene/SiO obtained in step (2) 2 The microspheres are mixed with 0.2g of graphene aqueous solution (wherein the mass percentage of graphene is 20%), and the mixture is reacted under stirring to obtain the polystyrene microspheres with graphene/polydopamine/silicon dioxide from inside to outside.
Example 4
The embodiment provides a graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere, and a preparation method thereof comprises the following steps:
(1) Preparation of O/W type Pickering emulsion: adding 0.5g of oleophylic modified nano-silica into deionized water, and performing ultrasonic dispersion to form uniformly dispersed SiO 2 An aqueous dispersion was prepared by adding 7g of a styrene monomer, 0.2g of divinylbenzene, and 0.276g of azobisisobutyronitrile to SiO 2 Emulsifying in water dispersion at high speed for 5 min with 20000r/min high speed emulsifier to obtain O/W type Pickering emulsion, transferring the obtained O/W type Pickering emulsion into three-neck flask, and adding N 2 Protecting for half an hour, heating to 70 deg.C, free radical polymerizing monomer styrene and divinylbenzene (cross-linking agent) in emulsion under the initiation of azodiisobutyronitrile to form polystyrene/SiO 2 And (3) microspheres.
(2) Dopamine modified polystyrene/SiO 2 Microsphere preparation: 2g of polystyrene/SiO 2 Washing and dispersing the microspheres in 100mL of pure water, adjusting the pH value to 8.5, then adding 0.024g of Tris (hydroxymethyl) aminomethane (Tris), ultrasonically dispersing uniformly and stirring, transferring the mixed solution into a three-neck bottle, then dropwise adding 0.1g of dopamine hydrochloride for reacting for 24 hours, centrifuging the obtained particles after the reaction is finished, removing unreacted reactants in the supernatant, and finally dispersing in water for later use.
(3) Preparing the graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere: 2g of dopamine modified polystyrene/SiO obtained in step (2) 2 The microspheres are mixed with 0.2g of graphene aqueous solution (wherein the mass percentage of graphene is 1%), and the mixture is reacted under stirring to obtain the polystyrene microspheres with graphene/polydopamine/silicon dioxide from inside to outside.
Comparative example 1
The comparative example provides a graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere, and the preparation method comprises the following steps:
(1) Preparation of O/W type Pickering emulsion: adding 0.5g of oleophylic modified nano silicon dioxide into deionized water, and performing ultrasonic dispersion to form uniformly dispersed SiO 2 An aqueous dispersion was prepared by adding 7g of a styrene monomer, 0.2g of divinylbenzene, and 0.276g of azobisisobutyronitrile to SiO 2 In aqueous dispersion, at 20000r/minEmulsifying at high speed for 5 minutes by a high-speed emulsifying machine to form O/W type Pickering emulsion, and transferring the O/W type Pickering emulsion into a three-neck flask, N 2 Protecting for half an hour, heating to 70 deg.C, free radical polymerizing monomer styrene and divinylbenzene (cross-linking agent) in emulsion under the initiation of azodiisobutyronitrile to form polystyrene/SiO 2 And (3) microspheres.
(2) Dopamine modified polystyrene/SiO 2 Microsphere preparation: 2g of polystyrene/SiO 2 Washing and dispersing the microspheres in 100mL of pure water, adjusting the pH value to 8.5, then adding 0.024g of Tris (hydroxymethyl) aminomethane (Tris), ultrasonically dispersing uniformly and stirring, transferring the mixed solution into a three-necked bottle, then dropwise adding 0.2g of dopamine hydrochloride for reacting for 24 hours, and after the reaction is finished, centrifuging the obtained particles to remove unreacted reactants in the supernatant to obtain the poly-dopamine/silicon dioxide polystyrene microspheres.
The examples and comparative example 1 were subjected to performance testing:
the test method comprises the following steps:
particle size: analyzing the particle size of the microspheres by using a laser particle sizer, wherein the standard is as follows: GB/T19077-2016;
thermal performance test criteria: GB/T19466.2-2004 plastic Differential Scanning Calorimetry (DSC);
mechanical property test standard: determination of tensile Properties of GB/T1040.3-2006 part 3: test conditions for films and sheets.
The test results are shown in table 1 below:
TABLE 1
Particle size (. Mu.m) Glass transition temperature (. Degree. C.) Tensile strength (Mpa)
Example 1 5～10 250～280 68.2
Comparative example 1 3～9 210～240 50.8
The SEM image of the graphene/silica double hybrid wall material modified polystyrene microsphere of example 1 is shown in fig. 1.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.

Claims (6)

1. A preparation method of a graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere is characterized by comprising the following steps:
(a) Dispersing oleophylic modified nano silicon dioxide in water, and then adding styrene monomer, cross-linking agent and initiator into the obtained dispersion liquidEmulsifying to obtain O/W type emulsion; polymerizing the O/W type emulsion to obtain polystyrene/SiO 2 Microspheres; the mass ratio of the styrene monomer to the cross-linking agent to the initiator is 5 to 10:0.2:0.1 to 0.5; the oleophylic modified nano silicon dioxide accounts for 0.5 to 2 percent of the mass of the styrene monomer;
(b) Mixing the polystyrene/SiO 2 Dispersing the microspheres in water to obtain a microsphere dispersion liquid; mixing the microsphere dispersion liquid with dopamine salt under the condition that the pH range is 7~9, and carrying out polymerization reaction on the obtained mixed liquid to obtain intermediate microspheres; polystyrene/SiO in the microsphere dispersion 2 The mass ratio of the microspheres to the dopamine salt is 10 to 1-20;
(c) Mixing the intermediate microspheres with an aminated graphene aqueous dispersion, and carrying out a grafting reaction; the mass of graphene in the graphene aqueous dispersion is 0.1 to 2 percent of that of the intermediate microsphere;
the graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere comprises a polystyrene microsphere, and a silicon dioxide layer and a graphene layer which are sequentially coated on the surface of the polystyrene microsphere; the silicon dioxide layer is connected with the graphene layer through a polydopamine layer.
2. The preparation method of the graphene/silica double-hybrid wall material modified polystyrene microsphere according to claim 1, wherein in the step (a), the cross-linking agent is selected from: at least one of divinylbenzene, N-methylolacrylamide, acrylic acid and hydroxyethyl acrylate; and/or the presence of a catalyst in the reaction mixture,
in step (a), the initiator is selected from: at least one of azodiisobutyronitrile, benzoyl peroxide and potassium persulfate.
3. The preparation method of the graphene/silica double-hybrid wall material modified polystyrene microsphere as claimed in claim 1, wherein in the step (a), the oleophylic modified nano silica is silane coupling agent modified nano silica, and the particle size of the nano silica is 10 to 20nm.
4. The preparation method of the graphene/silica double-hybrid wall material modified polystyrene microsphere as claimed in claim 3, wherein the silane coupling agent accounts for 0.5 to 10% of the mass of the nano silica, and is selected from the group consisting of: at least one of KH550, KH560 and KH 570.
5. A graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere is characterized in that the polystyrene microsphere is prepared by the preparation method of any one of claims 1 to 4.
6. The graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere as claimed in claim 5, wherein the particle size is 5-10 microns, and the glass transition temperature is 250-280 ℃.
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