WO2021246859A1 - Procédé de préparation de graphène fonctionnalisé par silane - Google Patents

Procédé de préparation de graphène fonctionnalisé par silane Download PDF

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Publication number
WO2021246859A1
WO2021246859A1 PCT/MY2020/050182 MY2020050182W WO2021246859A1 WO 2021246859 A1 WO2021246859 A1 WO 2021246859A1 MY 2020050182 W MY2020050182 W MY 2020050182W WO 2021246859 A1 WO2021246859 A1 WO 2021246859A1
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WO
WIPO (PCT)
Prior art keywords
solution
graphene
alkoxysilane
dihydrolevoglucosenone
functionalized graphene
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Application number
PCT/MY2020/050182
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English (en)
Inventor
Syed Muhammad Hafiz SYED MOHD JAAFAR
Hing Wah Lee
Suraya Sulaiman
Aiman Sajidah ABD AZIZ
Nora'zah Abdul Rashid
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Mimos Berhad
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Publication date
Application filed by Mimos Berhad filed Critical Mimos Berhad
Publication of WO2021246859A1 publication Critical patent/WO2021246859A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment

Definitions

  • the present invention relates to a method of preparing functionalized graphene, more particularly to a method of preparing silane-functionalized graphene using a biodegradable solvent.
  • Graphene an allotrope of carbon, is one atom thick and probably the strongest known material. Graphene is also light and conductive. Approaches are being made to tap the properties of graphene by fine tuning the chemical compatibility of graphene by introducing functional groups.
  • Silane is a versatile functional material to form a durable bond between organic and inorganic materials.
  • Surfaces of graphene can be modified by silane to a desired heterogeneous environment to incorporate different properties into a uniform composite structure.
  • Surface functionalization of silane on graphene surface can be made organophilic to infuse graphene properties in goods.
  • Functionalized reduced graphene oxide can be prepared with Hummer’s method.
  • the method involves creating derivatives containing traces of oxygen functional groups.
  • Toxic chemicals such as potassium permanganate, dimethylformamide, n-methyl-2-pyrrolidone, dimethylacetamide, tetrahydrofuran and hydrazine are used in the reduction of graphene oxide.
  • CN102351174A describes a method of preparing dispersible silane-functionalized graphene.
  • the method involves ultrasonic dispersion of graphene oxide in ethyl alcohol between room temperature to 78 o C, silane addition, centrifugation, and hydrazine hydrate addition.
  • the silane functionalized graphene has good dispersibility in solvents like tetrahydrofuran.
  • the mass ratio of graphene oxide to silane is 1:0.1-5.0.
  • CN102642830A discloses a method for preparing graphene modified by silane coupling agent.
  • the method includes adding graphite oxide and silane into reaction solvent between 0 o C to 90 o C.
  • the graphite oxide is grafted with silane.
  • the oxide is added into a reduction solvent with a reducer to obtain graphene powder modified by silane.
  • the mass ratio of graphite oxide to silane is 1:0.1-5.0.
  • US9290524B2 shows a method for producing functionalized graphene from graphite oxide.
  • Graphite oxide is mixed with at least one functionalizing compound in the presence of at least one first ionic liquid.
  • the mixture is sonicated to form exfoliated graphene oxide.
  • the exfoliated graphene oxide is refluxed to form functionalized graphene.
  • a method to prepare silane-functionalized graphene using biodegradable solution is presented.
  • Graphene nanoplatelets and organic peroxide is mixed in dihydrolevoglucosenone solution at room temperature to 60 o C.
  • Dihydrolevoglucosenone solution is a biodegradable solution, known as Cyrene trademark.
  • Alkoxysilane is added to the solution at 60 to 90 o C.
  • the solution is sonicated with ultrasonic waves using low heat at 60 to 70 o C.
  • the solution is washed with polar solvent.
  • the solution is dried to obtain alkoxysilane functionalized powder.
  • the solution is prepared using 2-4% wt. graphene nanoplatelets, 1-15% wt. peroxide, and 87-95% wt. dihydrolevoglucosenone.
  • the preferred peroxide is benzyl peroxide.
  • the concentration of dihydrolevoglucosenone is 1.25 g/ml.
  • 2-4% v/v alkoxysilane to the solution is added.
  • the preferred polar solvent is ethanol.
  • the present invention provides a method of preparing silane-functionalized graphene. Minimal heat is involved to prepare the functionalized graphene and a biodegradable solvent is used.
  • the main raw materials are graphene nanoplatelets (GNP), organic peroxide, dihydrolevoglucosenone and alkoxysilane.
  • GNP refers to host material. Lateral flake size 1 to 5,000 nm is used. The thickness of GNP is 0.3 to 500 nm. GNP used is preferably xGnP® - Grade H, purchased from XG Sciences Inc. and have an average thickness of approximately 15 nm, surface area of 50 to 80 m 2 /g with 5 ⁇ m particle size. The oxygen content presence in bulk GNP powder is ⁇ 1% and having residual acid content of ⁇ 0.5 wt%.
  • Organic peroxide is an oxidant and bleaching agent.
  • BPO Benzyl Peroxide
  • BPO Benzyl Peroxide
  • One of the method to produce a simple and controllable chemical modification is by exposing graphene with peroxide to create active site for functionalization to take place, thus eliminate the reduction process used by Hummers method.
  • the process relies on the immobilization of peroxide radical (i.e. phenyl free radicals) at the surface of graphene, followed by in situ surface-initiated polymerization to generate tethered polymer chain (e.g. alkoxysilane).
  • peroxide radical i.e. phenyl free radicals
  • the chemical functionalization could be easily controlled by adjusting the reaction temperature and quantity of peroxide used, thus being a single-step chemical reaction, needing no additives or catalysts and cost-effective.
  • Dihydrolevoglucosenone is a biodegradable aprotic dipolar solvent. It can be used as alternative polar solvent to dimethlformadide (DMF) and N-methly-2-pyrrolidone (NMP). Dihydrolevoglucosenone has great dispersive ability for graphene solutions. Dihydrolevoglucosenone is available under Cyrene trademark with density 1.25 g/ml.
  • Alkoxysilane refers to chemically reactive silane compounds with various organofunctional groups. Examples of alkoxysilanes are polydimethyloxysiloxane, methyltrimethoxysilane, vinyltriethoxysilane, alkytrialkoxysilane and tetraethoxysilane.
  • GNP and BPO are mixed into Cyrene solution at 2-4% wt. GNP, 1-15% wt. BPO and 87-95% wt. Cyrene.
  • Stirring is performed at 1,000 rpm in a three neck round bottom flask at room temperature to 60 o C.
  • a preferred mixture involves 3% wt. GNP, 3.7% wt. BPO and 93.3% wt. Cyrene at 50 o C.
  • Nitrogen gas is purged for 15 min to eliminate moisture. Any inert gas can be used in place of nitrogen gas.
  • Alkoxysilane solution such as vinyltriethoxysilane
  • the reaction is performed at temperature 60 to 90 o C and left for 24 hours. After that, the mixture is stirred and cooled to room temperature.
  • Any alkoxysilane solution can be used.
  • a ratio of 0.1-5% v/v alkoxysilane to the graphene solution is used.
  • a preferred ratio involves 3% v/v alkoxysilane.
  • the functionalization process takes place at the surface of the graphene.
  • the graphene mixture is sonicated with ultrasonic waves for twelve hours to disperse functionalized graphene.
  • Alkoxysilane-functionalized graphene are dispersed in this step.
  • the flake size of functionalized graphene is also reduced as a consequent of this step.
  • Polar solvent such as ethanol is used to wash excess alkoxysilane. Volume ratio of ethanol to graphene solution is 1:15. Elution is needed to extract functionalized graphene from undesired reactant solvent. The graphene solution is dried in an oven at 60 o C overnight to obtain alkoxysilane functionalized graphene powder.
  • FIG. 1 shows the chemical structure of alkoxysilane-functionalized graphene with vinyl organofunctional group.
  • the pendant unreacted organofunctional groups, such as vinyl, of the silane provides a route to crosslink the functionalized graphene network structure to other moieties which includes grafting to various polymer matrices.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

La présente invention concerne un procédé de préparation de graphène fonctionnalisé à l'aide d'un solvant biodégradable. Des nanoplaquettes de graphène et du peroxyde organique sont mélangés dans une solution de dihydrolévoglucosénone, à température ambiante à 60 °C. Une solution de dihydrlévoglucosénone, également connue sous la marque de commerce Cyrene, est une solution biodégradable. Un alcoxysilane est ajouté à la solution à 60 à 90 °C. La solution est soniquée avec des ondes ultrasonores. Le mélange est lavé avec un solvant polaire. La solution est séchée pour obtenir du graphène fonctionnalisé par alcoxysilane. Le procédé global implique une chaleur minimale.
PCT/MY2020/050182 2020-06-03 2020-11-30 Procédé de préparation de graphène fonctionnalisé par silane WO2021246859A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
MYPI2020002816 2020-06-03
MYPI2020002816 2020-06-03

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WO2021246859A1 true WO2021246859A1 (fr) 2021-12-09

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102351174A (zh) * 2011-08-23 2012-02-15 华南理工大学 一种可分散性硅烷功能化石墨烯的制备方法
JP2016210628A (ja) * 2015-04-28 2016-12-15 株式会社ダイセル 炭素材料の酸化方法並びに酸化グラフェン及び組成物
WO2019207305A1 (fr) * 2018-04-25 2019-10-31 Talga Technologies Limited Composite de graphène pré-imprégné

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102351174A (zh) * 2011-08-23 2012-02-15 华南理工大学 一种可分散性硅烷功能化石墨烯的制备方法
JP2016210628A (ja) * 2015-04-28 2016-12-15 株式会社ダイセル 炭素材料の酸化方法並びに酸化グラフェン及び組成物
WO2019207305A1 (fr) * 2018-04-25 2019-10-31 Talga Technologies Limited Composite de graphène pré-imprégné

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SALAVAGIONE, H. J. ET AL.: "Identification of high performance solvents for the sustainable processing of graphene", GREEN CHEMISTRY, vol. 19, 2017, pages 2550 - 2560, XP055449852, DOI: 10.1039/C7GC00112F *

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