An efficient way to functionalize graphene sheets with presynthesized polymer via ATNRC chemistry

Graphene nanosheets offer intriguing electronic, thermal and mechanical properties and are expected to find a variety of applications in high‐performance nanocomposite materials. The great challenge of exfoliating and dispersing pristine graphite or graphene sheets in various solvents or matrices can be achieved by facilely and properly chemical functionalization of the carbon nanosheets. Here we reported an efficient way to functionalize graphene sheets with presynthesized polymer via a combination of atom transfer nitroxide radical coupling chemistry with the grafting‐onto strategy, which enable us to functionalize graphene sheets with well‐defined polymer synthesized via living radical polymerization. A radical scavenger species, 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO), was firstly anchored onto ? COOH groups on graphene oxide (GO) to afford TEMPO‐functionalized graphene sheets (GS‐TEMPO), meanwhile, the GO sheets were thermally reduced. Next, GS‐TEMPO reacted with Br‐terminated well‐defined poly(N‐isopropylacrylamide) (PNIPAM) homopolymer, which was presynthesized by SET‐LRP, in the presence of CuBr/N,N,N′,N′,N″‐pentamethyldiethylenetriamine to form PNIPAM‐graphene sheets (GS‐PNIPAM) nanocomposite in which the polymers were covalently linked onto the graphene via the alkoxyamine conjunction points. The PNIPAM‐modified graphene sheets are easily dispersible in organic solvents and water, and a temperature‐induced phase transition was founded in the water suspension of GS‐PNIPAM. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Polymer brushes grafted from graphene via bioinspired polydopamine chemistry and activators regenerated by electron transfer atom transfer radical polymerization

Polymer brushes decorated reduced GO (rGO) with advanced applications have been prepared by bioinspired polydopamine (PDA) chemistry integrated with activators regenerated by electron transfer atom transfer radical polymerization (ARGET‐ATRP) technique. First, rGO/PDA was obtained by the process for graphene oxide (GO) coated with a homogeneous bio‐adhesive PDA layer. Then the initiator 2‐bromoisobutyryl bromide (BIBB) was immobilized on the surface of PDA functionalized rGO. Finally, rGO/PDA‐Br was polymerized with N, N‐diethylaminoethyl methacrylate (DEAEMA) and glycidyl methacrylate (GMA) to obtain rGO/PDA‐g‐polymer brushes by ARGET‐ATRP process. The prepared rGO/PDA‐g‐PGMA brush would be subjected to further functionalization with ethylenediamine (EDA), which would impart the obtained products (rGO/PDA‐g‐PGMA‐NH₂) with good adsorption ability toward cationic dyes. The chemical structures and morphologies of the functionalized GO products have been characterized in detail by Fourier transform infrared spectroscopy (FTIR), X‐ray photoelectron spectroscopy (XPS), Raman spectroscopy, thermal gravimetric analysis (TGA), scanning electron microscope (SEM), transmission electron microscope(TEM), and atomic force microscopy (AFM). The distinctive pH‐responsive character of rGO/PDA‐g‐PDEAEMA and adsorption ability of rGO/PDA‐g‐PGMA‐NH₂ for cationic dyes have been explored by UV–vis spectrophotometer. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 689–698     

Graphite Oxides: Effects of Permanganate and Chlorate Oxidants on the Oxygen Composition

Research on graphene materials has refocused on graphite oxides (GOs) in recent years. The fabrication of GO is commonly accomplished by using concentrated sulfuric acid in conjunction with: a) fuming nitric acid and KClO₃ oxidant (Staudenmaier); b) concentrated nitric acid and KClO₃ oxidant (Hofmann); c) sodium nitrate for in situ production of nitric acid in the presence of KMnO₄ (Hummers); or d) concentrated phosphoric acid with KMnO₄ (Tour). These methods have been used interchangeably in the graphene community, since the properties of GOs produced by these different methods were assumed as almost similar. In light of the wide applicability of GOs in nanotechnology applications, in which presence of certain oxygen functional groups are specifically important, the qualities and functionalities of the GOs produced by using these four different methods, side‐by‐side, was investigated. The structural characterizations of the GOs would be probed by using high resolution X‐ray photoelectron spectroscopy, nuclear magnetic resonance, Fourier transform infrared spectroscopy, and Raman spectroscopy. Further electrochemical applicability would be evaluated by using electrochemical impedance spectroscopy and cyclic voltammetry techniques. Our analyses highlighted that the oxidation methods based on permanganate oxidant (Hummers and Tour methods) gave GOs with lower heterogeneous electron‐transfer rates and a higher amount of carbonyl and carboxyl functionalities compared with when using chlorate oxidant (Staudenmaier and Hofmann methods). These observations indicated large disparities between the GOs obtained from different oxidation methods. Such insights would provide fundamental knowledge for fine tuning GO for future applications.     

Covalent polymeric modification of graphene nanosheets via surface‐initiated single‐electron‐transfer living radical polymerization

Graphene nanosheets offer intriguing electronic, thermal, and mechanical properties and are expected to find a variety of applications in high‐performance nanocomposite materials. Dispersal of graphene nanosheets in polymer hosts and precise interface control are challenging due to their strong interlayer cohesive energy and surface inertia. Here, an efficient strategy is presented for growing polymers directly from the surface of reduced graphene oxide (GO). This method involves the covalent attachment of Br‐containing initiating groups onto the surface of hydrazine hydrate reduced GO via a diazonium addition and the succeeding linking of poly(tert‐butyl methacrylate) (PtBMA) chains (71.7 wt % grafting efficiency) via surface‐initiated single‐electron‐transfer living radical polymerization (SET‐LRP) to graphene nanosheets. The resulting materials were characterized by using a range of testing techniques and it was proved that polymer chains were successfully introduced to the surface of exfoliated graphene sheets. After grafting with PtBMA, the modified graphene sheets still maintained the separated single layers, and the dispersibility was improved significantly. The method is believed to offer possibilities for optimizing the processing properties and interface structure of graphene–polymer nanocomposites. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Modification of graphene/graphene oxide with polymer brushes using controlled/living radical polymerization

Graphene nanosheets possess a range of extraordinary physical and electrical properties with enormous potential for applications in microelectronics, photonic devices, and nanocomposite materials. However, single graphene platelets tend to undergo agglomeration due to strong π–π and Van der Waals interactions, which significantly compromises the final material properties. One of the strategies to overcome this problem, and to increase graphene compatibility with a receiving polymer host matrix, is to modify graphene (or graphene oxide (GO)) with polymer brushes. The research to date can be grouped into approaches involving grafting‐from and grafting‐to techniques, and further into approaches relying on covalent or noncovalent attachment of polymer chains to the suitably modified graphene/GO. The present Highlight article describes research efforts to date in this area, focusing on the use of controlled/living radical polymerization techniques. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Polymer coating of graphene oxide via reversible addition–fragmentation chain transfer mediated emulsion polymerization

This work describes a versatile method to encapsulate graphene oxide (GO) with polymers using reversible addition‐fragmentation chain transfer (RAFT) mediated emulsion polymerization. A living low molecular weight anionic macro‐RAFT statistical copolymer of sodium styrene sulfonate, acrylic acid, and butyl acrylate (BA) was synthesized using 2‐{[(butylsulfanyl)carbonothioyl] sulfanyl} propanoic acid as the chain transfer agent. GO was dispersed in water by pretreating the surface with poly(allylamine hydrochloride) (PAH), before being stabilized by the addition of the anionic macro‐RAFT copolymer. PAH was used to facilitate the adsorption of the macro‐RAFT copolymer to the GO surface via electrostatic attraction between opposite charges. The dispersed GO sheets were encapsulated with polymer by the free radical emulsion polymerization of methyl methacrylate and BA under starved fed conditions. The polymer shells encapsulating the GO sheets were formed by the chain extension of the adsorbed living macro‐RAFT copolymer. TEM, SEM, FTIR, and AFM were used to confirm the presence of the polymer layer on the surface of the GO. The thickness of the polymer coating can be adjusted by controlling the amount of monomer fed into the system. Partial polymer coatings of the GO could be achieved by varying the amount of PAH. The encapsulated GO was found to be easily dispersed in both aqueous and organic solvents over a range of polarities. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1413–1421     

Polymer brushes on multiwalled carbon nanotubes by activators regenerated by electron transfer for atom transfer radical polymerization

The synthesis and characterization of multiwalled carbon nanotube (MWCNT) polymer brushes produced by activators regenerated by electron transfer (ARGET) in atom‐transfer radical polymerization (ATRP) was discussed. The polymer brushes were synthesized by esterification of the MWCNT carboxylic acid groups with hydroxyethyl‐2‐bromoisobutyrate and subsequently used in ARGET ATRP. This created a well defined living polymer brush carbon nanotube of comparatively low polydispersity and a polymer layer 10 nm thick. As, ARGET ATRP uses only minute concentrations of copper (II) catalyst, and is less sensitive to air compared to other living polymerization techniques, this process is a more industry‐compatible route for the commercialization of such materials. The structural and chemical properties were explored by a range of techniques including high resolution transmission electron microscopy, gel permeation chromatography, elemental analysis, Fourier transform infrared spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. In addition, the polymer brush nanotubes were explored for their potential use in films and as fillers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Building nanostructures using RAFT polymerization

Reversible addition fragmentation chain transfer (RAFT) polymerization is one of the most extensively studied controlled/living radical polymerization methods that has been used to prepare well‐defined nanostructured polymeric materials. This review, with more 650 references illustrates the range of well‐defined functional nanomaterials that can be accessed using RAFT chemistry. The detailed syntheses of macromolecules with predetermined molecular weights, designed molecular weight distributions, controlled topology, composition and functionality are presented. RAFT polymerization has been exploited to prepare complex molecular architectures, such as stars, blocks and gradient copolymers. The self‐assembly of RAFT‐polymer architectures has yielded complex nanomaterials or in combination with other nanostructures has generated hybrid multifunctional nanomaterials, such as polymer‐functionalized nanotubes, graphenes, and inorganic nanoparticles. Finally nanostructured surfaces have been described using the self‐organization of polymer films or by the utilization of polymer brushes. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Self‐assembly of star‐shaped polystyrene‐block‐polypeptide copolymers synthesized by the combination of atom transfer radical polymerization and ring‐opening living polymerization of α‐amino acid‐N‐carboxyanhydrides

The self‐assembling nature and phase‐transition behavior of a novel class of triarm, star‐shaped polymer–peptide block copolymers synthesized by the combination of atom transfer radical polymerization and living ring‐opening polymerization of α‐amino acid‐N‐carboxyanhydride are demonstrated. The two‐step synthesis strategy adopted here allows incorporating polypeptides into the usual synthetic polymers via an amido–amidate nickelacycle intermediate, which is used as the macroinitiator for the growth of poly(γ‐benzyl‐L ‐glutamate). The characterization data are reported from analyses using gel permeation chromatography and infrared, ¹H NMR, and ¹³C NMR spectroscopy. This synthetic scheme grants a facile way to prepare a wide range of polymer–peptide architectures with perfect microstructure control, preventing the formation of homopolypeptide contaminants. Studies regarding the supramolecular organization and phase‐transition behavior of this class of polymer‐block‐polypeptide copolymers have been accomplished with X‐ray diffraction, infrared spectroscopy, and thermal analyses. The conformational change of the peptide segment in the block copolymer has been investigated with variable‐temperature infrared spectroscopy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2774–2783, 2006     

Light‐driven atom transfer radical polymerization on supramolecular complexes of conjugated polymers and single‐walled carbon nanotubes

Previous approaches used to decorate latently reactive conjugated polymer‐coated carbon nanotube complexes have utilized “grafting‐to” strategies. Here, we coat the carbon nanotube surface with a conjugated polymer whose side chains contain the radical initiator, α‐bromoisobutyrate, which enables atom transfer radical polymerization (ATRP) from the polymer–nanotube surface. Using light to generate Cu(I) in situ, ATRP is used to grow narrow dispersity polymer chains from the polymer–nanotube surface. We confirm the successful polymerization of (meth)acrylates from the polymer–nanotube surface using a combination of gel permeation chromatography and infrared spectroscopy. Strikingly, we demonstrate that nanotube optoelectronic properties are preserved after radical‐mediated polymer grafting using Raman spectroscopy and photoluminescence mapping. Overall, this work elucidates a method to grow narrow dispersity polymer chains from the polymer–nanotube surface using light‐driven radical chemistry, with concurrent preservation of nanotube optoelectronic properties. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2015–2020     

Functionalization of graphene oxide towards thermo‐sensitive nanocomposites via moderate in situ SET‐LRP

A mild and efficient strategy is presented for growing thermo‐sensitive polymers directly from the surface of exfoliated graphene oxide (GO). This method involves the covalent attachment of Br‐containing initiating groups onto the surface of GO sheets followed by in situ growing poly[poly(ethylene glycol) ethyl ether methacrylate] (PPEGEEMA) via single‐electron‐transfer living radical polymerization (SET‐LRP). Considering the lack of reactive functional groups on the surface of GO, exfoliated GO sheets were subjected to an epoxide ring opening reaction with tris(hydroxymethyl) aminomethane (TRIS) at room temperature. The initiating groups were grafted onto TRIS‐GO sheets by treating hydroxyls with 2‐bromo‐2‐methylpropionyl bromide at room temperature. PPEGEEMA chains were synthesized by in situ SET‐LRP using CuBr/Me₆TREN as catalytic system at 40 °C in H₂O/THF. The resulting materials were characterized using a range of testing techniques and it was proved that polymer chains were successfully introduced to the surface of GO sheets. After grafting with PPEGEEMA, the modified GO sheets still maintained the separated single layers and the dispersibility was significantly improved. This TRIS‐GO‐PPEGEEMA hybrid material shows reversible self‐assembly and deassembly in water by switching temperature at about 34 °C. Such smart graphene‐based materials promise important potential applications in thermally responsive nanodevices and microfluidic switches. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Endoperoxides Revealed as Origin of the Toxicity of Graphene Oxide

Potential biomedicinal applications of graphene oxide (GO), for example, as a carrier of biomolecules or a reagent for photothermal therapy and biosensing, are limited by its cytotoxicity and mutagenicity. It is believed that these properties are at least partially caused by GO‐induced oxidative stress in cells. However, it is not known which chemical fragments of GO are responsible for this unfavorable effect. We generated four GOs containing variable redox‐active groups on the surface, including Mn²⁺, C‐centered radicals, and endoperoxides (EPs). A comparison of the abilities of these materials to generate reactive oxygen species in human cervical cancer cells revealed that EPs play a crucial role in GO‐induced oxidative stress. These data could be applied to the rational design of biocompatible nontoxic GOs for biomedical applications.     

ATNRC/SET‐NRC synthesis of graphene/polyisobutylene nanocomposites

Two polyisobutylene‐grafted graphene nanocomposites were prepared by CuBr‐catalyzed atom transfer nitroxide radical coupling (ATNRC) and Cu‐catalyzed single electron transfer‐nitroxide radical coupling (SET‐NRC) chemistry under mild conditions, respectively, through the grafting‐onto strategy. Graphene oxide was first reduced to graphene by diazonium addition reaction followed by treating graphene with ethyl 2‐bromoisobutyrate for introducing Br‐containing groups onto the surface to give G‐Br. The presynthesized well‐defined functional polyisobutylene (PIB) possessing 2,2,6,6‐tetramethylpiperidine‐1‐oxyl terminal group obtained via cationic polymerization of isobutylene was then coupled with G‐Br through ATNRC or SET‐NRC at room temperature to afford polymer‐modified graphene, G‐PIB. SET‐NRC method has a faster coupling rate using cheaper reagent (Cu wire instead of CuBr) in comparison with ATNRC approach. Detailed characterizations including FT‐IR, Raman, ¹H NMR, TGA, AFM, and TEM assured us of successful anchoring of PIB chains onto the surface of graphene sheets. The resulting G‐PIB nanocomposites still maintain the separated single layers in dispersion and the dispersibilities in organic solvents are significantly improved. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4505–4514     

Surface Modification of Graphene Oxides by Plasma Techniques and Their Application for Environmental Pollution Cleanup

Graphene oxides (GOs) have come under intense multidisciplinary study because of their unique physicochemical properties and possible applications. The large amount of oxygen‐containing functional groups on GOs leads to a high sorption capacity for the removal of various kinds of organic and inorganic pollutants from aqueous solutions in environmental pollution cleanup. However, the lack of selectivity results in difficulty in the selective removal of target pollutants from aqueous solutions in the presence of other coexisting pollutants. Herein, the surface grafting of GOs with special oxygen‐containing functional groups using low‐temperature plasma techniques and the application of the surface‐modified GOs for the efficient removal of organic and inorganic pollutants in environmental pollution are reviewed. This paper gives an account of our research on the application of GO‐based nanomaterials in environmental pollution cleanup, including: (1) the synthesis and surface grafting of functional groups on GOs, summarizing various types of low‐temperature plasma techniques for the synthesis of graphene/GOs; and (2) the application of graphene/GOs and their composites for the efficient removal of organic and inorganic pollutants from aqueous solutions, including the interaction mechanism according to recently published results.     

Controlled synthesis of fluorinated copolymers with pendant sulfonates

Novel, fluorinated copolymers with different architectures bearing sulfopropyl groups were synthesized in a three‐step procedure. The first step involved atom transfer radical polymerization (ATRP) of aromatic fluorinated monomers followed by two modification reactions performed on the polymer chain: demethylation and sulfopropylation. As a result two types of fluorinated copolymers were obtained. The first one was synthesized by ATRP of 2,3,5,6‐tetrafluoro‐4‐methoxystyrene (TFMS). After the modification steps copolymers with randomly distributed sulfopropyl groups along the backbone were obtained. The second type of copolymers has diblock architecture with one of the blocks being sulfopropylated. They were synthesized via ATRP of 2,3,4,5,6‐pentafluorostyrene (FS) initiated by a PTFMS‐macroinitiator followed by demethylation and sulfopropylation of the TFMS‐block. The copolymers were characterized by size‐exclusion chromatography, FTIR, and ¹H NMR spectroscopy. Their thermal properties were investigated by differential scanning calorimetry and thermal gravimetric analyses. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7827–7834, 2008     

Enhanced adsorption performance of the graphene oxide with metallic ion impurities by elution

The graphene oxides (GOs) with various content of metallic ions impurities were prepared, and the adsorption performance of the GO before and after elution was evaluated. The prepared GOs were characterized by X‐ray diffraction, Fourier transform infrared spectroscopy, inductively coupled plasma and atomic force microscopy. The results indicated that the metallic ion impurities hardly affected the interlayer distance, microstructure and thickness of the prepared GOs. The adsorption isotherm and adsorption kinetic results showed that the metallic ions adsorbed on the GO surface had a negative influence on both the adsorption capacity and rate. After eluted by HNO₃ or HCl, most of the metallic ions adsorbed on the GO‐91 surface were ion‐exchanged by the protons of the acid eluents, and the purified GO showed enhanced equilibrium capacities and improved adsorption rate. The elution efficiency of HCl was better than that of HNO₃, and the adsorption capacity and rate of the GO eluted by HCl approximately reached to those of the GO prepared from the graphite with high purity. It indicated that HCl could efficiently remove the metallic ions adsorbed on the GO surface. Copyright © 2017 John Wiley & Sons, Ltd.     

Thermoresponsive graphene oxide‐PNIPAM nanocomposites with controllable grafting polymer chains via moderate in situ SET–LRP

In this study, we report a mild and efficient strategy for growing thermosensitive polymers directly from the surface of exfoliated graphene oxide (GO). Exfoliated GO sheets were sequentially subject to the epoxide ring‐opening reaction with tris(hydroxymethyl) aminomethane (TRIS) to increase the amount of reactive sites, the esterification with 2‐bromo‐2‐methylpropionyl bromide to introduce the Br‐containing initiating groups, and the surface‐initiated single electron transfer–living radical polymerization of N‐isopropylacrylamide (NIPAM) to tune the molecular weights of grafted polymers. All these reactions were performed at ambient temperature without losing any other oxygen‐containing functionality on GO. The resulting TRIS‐GO‐PNIPAM nanocomposites still maintain the separated single layers in dispersion, and the dispersibilities in organic solvents are significantly improved. Meanwhile, the aqueous dispersion of TRIS‐GO‐PNIPAM shows reversible temperature switching self‐assembly and disassembly behavior at about 40°C. Such smart graphene‐based hybrid materials are promising for applications in nanoelectronics, sensors, and microfluidic switches. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Self‐assembled graphene oxide–gelatin nanocomposite hydrogels: Characterization,formation mechanisms,and pH‐sensitive drug release behavior

Novel physically crosslinked graphene oxide (GO)‐gelatin nanocomposite hydrogels were obtained by self‐assembly. The hydrogels with various ratios of GO to gelatin were prepared, and characterized by X‐ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, and scanning electron microscopy. The static and dynamic rheological properties of the hydrogels were investigated, along with the underlying hydrogel formation mechanisms. The storage modulus of the hydrogels (containing 98–98.5 wt % water) reached 114.5 kPa, owing to the relatively strong physical bonding (i.e., hydrogen bonding and electrostatic forces) between GO and gelatin. Drug release tests showed that the drug release from the hydrogel was pH‐dependent, with 96% of the model drug released in a neutral environment, compared to 28% released in an acidic medium. These hydrogels could have potential in pH‐sensitive drug delivery. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 356–367     

Modification of carboxyl‐functionalized single‐walled carbon nanotubes with biocompatible,water‐soluble phosphorylcholine and sugar‐based polymers: Bioinspired nanorods

We report here the successful functionalization of single‐walled carbon nanotubes with bioinspired sugar and phosphocholine polymeric structures via surface‐initiated atom transfer radical polymerization. The surface‐polymer‐coated carbon nanotubes have been systematically analyzed by Raman, infrared, ultraviolet–visible, and nuclear magnetic resonance spectroscopy and high‐resolution transmission electron microscopy, which give strong evidence of successful functionalization. The successful aqueous dispersion of the functionalized carbon nanotubes also indicates that functionalization has been achieved. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6558–6568, 2006     

Polymer end group modifications and polymer conjugations via “click” chemistry employing microreactor technology

This study presents the development of microreactor protocols for the successful continuous flow end group modification of atom transfer radical polymerization precursor polymers into azide end‐capped materials and the subsequent copper‐catalyzed azide alkyne click reactions with alkyne polymers, in flow. By using a microreactor, the reaction speed of the azidation of poly(butyl acrylate), poly(methyl acrylate), and polystyrene can be accelerated from hours to seconds and full end group conversion is obtained. Subsequently, copper‐catalyzed click reactions are executed in a flow reactor at 80 °C. Good coupling efficiencies are observed and various block copolymer combinations are prepared. Furthermore, the flow reaction can be carried out in only 40 min, while a batch procedure takes several hours to reach completion. The results indicate that the use of a continuous flow reactor for end group modifications as well as click reactions has clear benefits towards the development and improvement of well‐defined polymer materials. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1263–1274