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.     

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     

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     

In situ Synthesis of Poly(methyl methacrylate)/Graphene Oxide Nanocomposites Using Thermal-initiated and Graphene Oxide-initiated Polymerization

A facile and cost-effective method to prepare poly(methyl methacrylate) (PMMA)/graphene oxide (GO) nanocomposites was developed by in situ polymerization. By using thermal-initiated and GO-initiated polymerization of methyl methacrylate (MMA), no extra radical initiator was added during the reaction. Without any pre-functionalization of GO, PMMA chains were covalently bonded to its surface, which was confirmed by Fourier-transform infrared, atomic force microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy investigations. TGA analysis showed that the mass ratio of grafted PMMA and GO was as high as 1.7. Transmission electron microscopy and X-ray powder diffraction investigations demonstrated that the grafting of PMMA chains to GO surfaces resulted in homogeneous dispersion of GO sheets in PMMA matrix, which led to a commendable performance on its mechanical and thermal properties. Dynamic mechanical analysis showed that, at a loading level of just 0.5 wt% for the nanocomposites, the storage modulus of the nanocomposites was improved 14%, and the glass transition temperature was increased 12°C in comparison with that of neat PMMA. Thermogravimetric analysis showed that the onset degradation temperature of the nanocomposites was increased 13°C with a GO content of 0.25 wt%.     

Functionalization of Graphene Sheets via Chemically Grafting of PMMA Chains Through in-situ Polymerization

In this work, we report the preparation of graphene nanoplatelet which covalently functionalized with PMMA chains by introduction of vinyl groups onto graphene surface through simple esterification reaction between hydroxyl groups of graphite oxide and methacrylic anhydride. The synthesis is followed by in-situ polymerization with MMA monomers. The structural properties were characterized with X-ray diffraction spectroscopy (XRD) and scanning electronic microscopy (SEM) that showed the crystalline graphite is converted to individual layers during the synthesis steps. The grafting of PMMA chains was monitored with IR spectroscopy (FT-IR) and thermogravimetric analysis (TGA). The TGA results revealed 40% wt of PMMA chains chemically grafted onto graphene surface. Significant increase in glass transition temperature (T_g) and existence of polymer chains in two positions (physically absorbed and chemically grafting onto graphite surface) are indicated by differential scanning calorimetric (DSC) analysis.     

Synthesis of polydopamine‐coated graphene–polymer nanocomposites via RAFT polymerization

Graphene‐polymer nanocomposites have significant potential in many applications such as photovoltaic devices, fuel cells, and sensors. Functionalization of graphene is an essential step in the synthesis of uniformly distributed graphene‐polymer nanocomposites, but often results in structural defects in the graphitic sp² carbon framework. To address this issue, we synthesized graphene oxide (GO) by oxidative exfoliation of graphite and then reduced it into graphene via self‐polymerization of dopamine (DA). The simultaneous reduction of GO into graphene, and polymerization and coating of polydopamine (PDA) on the reduced graphene oxide (RGO) surface were confirmed with XRD, UV–Vis, XPS, Raman, TGA, and FTIR. The degree of reduction of GO increased with increasing DA/GO ratio from 1/4 to 4/1 and/or with increasing temperature from room temperature to 60 °C. A RAFT agent, 2‐(dodecylthiocarbonothioylthio)?2‐methylpropionic acid, was linked onto the surface of the PDA/RGO, with a higher equivalence of RAFT agent in the reaction leading to a higher concentration of RAFT sites on the surface. Graphene‐poly(methyl methacrylate), graphene‐poly(tert‐butyl acrylate), and graphene‐poly(N‐isopropylacrylamide) nanocomposites were synthesized via RAFT polymerization, showing their characteristic solubility in several different solvents. This novel synthetic route was found facile and can be readily used for the rational design of graphene‐polymer nanocomposites, promoting their applications. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3941–3949     

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     

Synthesis and Characterization of Poly(methyl methacrylate)-b-Polystyrene/TiO2 Nanocomposites Via Reversible Addition-Fragmentation Chain Transfer Polymerization

A diblock copolymer, poly(methyl methacrylate)-b-polystyrene (PMMA-b-PS), was grafted onto the surface of nano-titania (nano-TiO₂) successfully via reversible addition-fragmentation chain transfer (RAFT) polymerization. The surface of TiO₂ nanoparticles was modified initially by attaching dithioester groups to the surface using silane coupling agent 3-(chloropropyl)triethoxy silane and sodium ethyl xanthate. The polymerization of methyl methacrylate and styrene were then initiated and propagated on the TiO₂ surface by RAFT polymerization. The resulting composite nanoparticles were characterized by means of XPS, FT-IR, ¹H NMR and TGA. The results confirmed the successful grafting of poly(methyl methacrylate) (PMMA) and diblock copolymer chains onto the surface of TiO₂. The amount of PMMA grafted onto the TiO₂ surface increased with the polymerization time. Moreover, the kinetic studies revealed that the ln([M]₀/[M]), where [M]₀ is the initial and [M] is the time dependent monomer concentrations, increased linearly with the polymerization time, indicating the living characteristics of the RAFT polymerization.     

Surface modification of polymeric microspheres using glycopolymers for biorecognition

We report the synthesis and characterization of sugar-containing microspheres consisting of poly(divinylbenzene) (PDVB) cores onto which chains of galactose- or mannose-bearing polymers have been grafted. PDVB particles prepared by distillation polymerization with a diameter of 2.4 μm containing residual surface vinyl groups were used as starting material. “Grafting from”, “grafting through” and “grafting to” techniques were performed and special interest was laid towards the resulting grafting densities. The surface modification via “grafting from” was conducted by reversible addition fragmentation chain transfer (RAFT) polymerization directly from the surface, whereas thiol-ene chemistry was used to affix glycopolymer chains onto the particle surface. The resulting sugar-covered microspheres were analyzed towards their protein recognition activity with a series of lectins.     

甲基丙烯酸聚乙二醇单甲醚酯在聚(醚-氨酯)表面的臭氧化接枝

甲基丙烯酸聚乙二醇单甲醚酯在聚（醚 氨酯）表面的臭氧化接枝王晨晖王安锋车波周彩华苏琳丽林思聪（南京大学高分子科学与工程系生物材料分子工程与控制释放分子工程室南京２１００９３）王炳坤（南京大学环境科学系南京２１００９３）关键词臭氧化，表面接枝，大...     

Poly(vinylphosphonate)s functionalized polymer microspheres via rare earth metal‐mediated group transfer polymerization

We demonstrate a facile, yet efficient method for the functionalization of crosslinked polystyrene (PS) microspheres with biocompatible poly(vinylphosphonate)s via the combination of a UV grafting polymerization and a surface‐initiated group transfer polymerization. Self‐initiated photografting and photopolymerization of ethylene glycol dimethacrylate results in direct photografting of poly(ethylene glycol dimethacrylate) on the PS microspheres with dangling methacrylate functionalities, which are used to immobilize ytterbocene complexes to form the surface‐bound rare‐earth metal catalyst system. The surface‐initiated GTP of dialkyl vinylphosphonates from the initiator system leads to the functionalization of PS microspheres with poly(vinylphosphonate) brushes. Polymerization kinetic investigation indicates that surface‐initiated GTP leads to a constant and remarkably rapid weight gain of the microsphere (a microsphere weight increase of 600% within 3 min), owing to the highly living and efficient character of GTP. The surface‐initiated GTP occurring inside the microsphere causes an accumulation of the tension between the polymer chains in the microsphere, which eventually induces fracture of the microsphere for longer polymerization time. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2919–2925     

Improving mechanical and electrical properties of poly(vinyl alcohol-<Emphasis Type="Italic">g</Emphasis>-acrylic acid) nanocomposite films by reinforcement of thermally reduced graphene oxide

Graphene has drawn an astounding research interest in recent years, owing to its exceptional properties. The scaled-up and trustworthy production of graphene derivatives, such as graphene oxide (GO) and thermally reduced graphene oxide (TRGO), offer wide variety of possibilities to synthesize graphene-based polymer materials for various applications. In the present work, poly(vinyl alcohol-g-acrylic acid) films were prepared by grafting polyacrylic acid chains onto polyvinyl alcohol backbone employing a free radical polymerization system in the presence of crosslinking agent, N,N′-methylenebisacrylamide (MBA). The graphene was homogeneously dispersed into the prepared polymer using thermal mechanical agitation technique. The so prepared nanocomposites were undertaken for structural and morphological characterization using FTIR, SEM, XRD, Raman Spectroscopy, DLS, Zetasizer and AFM analysis, respectively. The electrical conductive and mechanical properties of prepared nanocomposite films were also investigated.     

Grafting polymerization of single‐handed helical poly(phenyl isocyanide)s on graphene oxide and their application in enantioselective separation

We herein report a “grafting from” strategy to immobilize optically active helical poly(phenyl isocyanide)s onto graphene oxide (GO) nanosheets. After covalently bounding alkyne‐Pd(II) initiator onto GO nanosheets, the designed GO/polymer composites P1 @GO and P1 ‐b‐ P2 @GO featuring single‐handed helical poly(phenyl isocyanide)s growing from GO nanosheets were prepared by sequential addition of the chiral and achiral isocyanide monomers. Post‐synthetic hydrolysis rendered P1 ‐b‐ P3 @GO to improve the hydrophilicity. The successful covalent bonding of poly(phenyl isocyanide)s chains onto GO nanosheets was certified by several cross evidences including scan emission microscopy, atomic force microscopy, Raman spectroscopy, X‐ray photoelectron spectroscopy, and thermogravimetric analysis. Circular dichroism spectra proved that the chiral information was introduced through the grafted single‐handed helical polymer chains successfully. In addition, the resulting GO/polymer composites were explored as a chiral additive to induce enantioselective crystallization of racemic organic molecules. Preferential formation of rod‐like L‐alanine crystals was induced by composites bearing right‐handed helical poly(phenyl isocyanide)s. The enantiomeric excess value of the induced crystals reached 76%, displaying the potential in future applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2092–2103     

Layered silicate/polyester nanohybrids by controlled ring-opening polymerization

In this study, layered silicate/aliphatic polyester nanohybrids were synthesized by ring-opening polymerization of ϵ-caprolactone as promoted by the so-called coordination-insertion mechanism. These nanocomposites were formed in presence of montmorillonite surface-modified by ammonium cations bearing hydroxyl group(s), such as bis(2-hydroxyethyl)methyl (hydrogenated tallow alkyl) ammonium. The lactone polymerization could be initiated by all the hydroxyl functions available at the clay surface, after activation into either tin(II) or Al(III) alkoxide active species. Hybrid nanocomposites were accordingly generated through the covalent grafting of every polyester chain onto the filler surface. Surface-grafted polycaprolactone (PCL) chains were untied and isolated by ionic exchange reaction with LiCl in THF solution and molar masses were measured by size exclusion chromatography. The PCL molar masses could be controlled and readily tuned by the content of hydroxyl groups available at the clay surface. Interestingly, initiation reaction by aluminum trialkoxide active species yielded grafted PCL chains characterized by very narrow molecular weight distribution (M_w/M_n∼1.2). These polyester-grafted layered silicate nanohybrids displayed complete exfoliation of silicate sheets as shown by X-ray diffraction (XRD) and transmission electron microscopy (TEM).     

Preparation and characterization of monolithic column by grafting pH-responsive polymer

A novel modified monolithic column with pH-responsive polymer chains was prepared by grafting methacrylic acid onto the poly(glycidyl methacrylate-co-ethylene dimethacrylate) monolith. The grafting polymerization was achieved in an in situ manner which was performed by pumping methacrylic acid directly through an acidic hydrolysis monolithic column using potassium peroxydisulfate initiated free-radical polymerization. The grafted monolithic column was demonstrated to be the pH-responsive to the pore structure and the chromatographic characterization. The permeability of the column and the retention factors of five benzene homologues decreased due to the conformational changes of the polymer chains when the pH of mobile phase increased from 4.5 to 7.5. Furthermore, the modified monolithic column was used as the pH-responsive stationary phase and exhibited an excellent separation of four basic proteins.     

Effect of molecular interactions on the performance of poly(isobutylene-co-isoprene)/graphene and clay nanocomposites

Poly(isobutylene-co-isoprene) (IIR)/graphene and cloisite10A nanocomposites were prepared successfully and the resulting mechanical, rheological and barrier properties were carefully evaluated and compared. Chemical treatments like maleic anhydride grafting were used to improve the dispersion of the clay in the IIR matrix. Blends with different loading (20, 40, 60, and 80 %) of maleic anhydride grafted poly(isobutylene-co-isoprene) (MA-g-IIR) and IIR were made to maintain a balance between the beneficial polarity induced by MA grafting and the inevitable decrease in molecular weight (due to chain scission) induced by the free radical grafting process. The highest moduli, tensile strength and elongation at break were achieved in the case of a 60:40 ratio of MA-g-IIR (grafting degree 0.75)/IIR mixture with 5 phr of cloisite 10A. IIR/graphene nanocomposites exhibited higher reinforcement (Young’s moduli) and lower gas permeability compared to the optimized clay nanocomposites with same weight percentage. The filler–elastomer and filler–filler interactions deduced from rheology, stress relaxation and Payne effect experiments emphasize the reinforcing ability in IIR/graphene and MA-g-IIR/clay. XRD, SEM and TEM results further substantiated the results from the obtained micro structure of the nanocomposites. The improved performances of IIR/MA-g-IIR/clay and IIR/graphene were successfully correlated with interactions between the filler platelets and elastomer chains occurring in the nanocomposites.     

Thermosensitive graphene nanocomposites formed using pyrene‐terminal polymers made by RAFT polymerization

Thermosensitive graphene‐polymer composites have been prepared by attaching poly(N‐isopropylacrylamide) (PNIPAAm) onto the basal plane of graphene sheets via π‐π stacking. Pyrene‐terminated PNIPAAm was synthesized using reversible addition fragmentation chain transfer (RAFT) polymerization via a pyrene‐functional RAFT agent. Aqueous solutions of the graphene‐polymer composites were stable and thermosensitive. The lower critical solution temperature (LCST) of pyrene‐terminated PNIPAAm was measured to be 33 °C. When the pyrene‐functional polymer was attached to graphene the resultant composites were also thermosensitive in aqueous solutions exhibiting a reversible suspension behavior at 24 °C. Atomic force microscopy (AFM) analysis revealed that the thickness of a graphene‐PNIPAAm (M_n: 10,000 and PDI: 1.1) sheet was ～5.0 nm. The surface coverage of polymer chains on the graphene basal plane was calculated to be 7.2 × 10^?11 mol cm^?2. The graphene‐PNIPAAm composite material was successfully characterized using X‐ray photoelectron spectroscopy (XPS), attenuated total reflection infrared (ATR‐IR) spectroscopy, and thermogravimetric analysis (TGA). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 425–433, 2010     

Uni‐molecular nanoparticles of poly(2‐oxazoline) showing tunable thermoresponsive behaviors

Herein, cylindrical molecular bottlebrushes grafted with poly(2‐oxazoline) (POx) as a shaped tunable uni‐molecular nanoparticle were synthesized via the grafting‐onto approach. First, poly(glycidyl methacrylate) (PGMA) backbones with azide pendant units were prepared via reversible addition fragmentation transfer (RAFT) polymerization followed by post‐modification. The degree of polymerization (DP) of the backbones was tuned in a range from 20 to 800. Alkynyl‐terminated POx side chains were synthesized by living cationic ring opening polymerization (LCROP) of 2‐ethyl‐2‐oxazoline (EtOx) and 2‐methyl‐2‐oxazoline (MeOx), respectively. The DP of side chains was varied between 20 and 100. Then, the copper‐catalyzed azide‐alkynyl cycloaddition (CuAAC) click chemistry was conducted with a feed ratio of [alkynyl]:[azide] = 1.2:1 to yield a series of brushes. Depending on the DP of side chains, the grafting density ranged between 47 and 85%. The resulting brushlike nanoparticles exhibited shapes of sphere, rod and worm. Aqueous solutions of PEtOx brushes demonstrated a thermoresponsive behavior as a function of the length of backbones and side chains. Surprisingly, it was found that the lower critical solution temperature of PEtOx brushes increased with a length increase of backbones. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 174–183     

Electrical conductivity of poly(ethylene terephthalate)/expanded graphite nanocomposites prepared by in situ polymerization

Nanocomposites based on poly(ethylene terephthalate) (PET) and expanded graphite (EG) have been prepared by in situ polymerization. Morphology of the nanocomposites has been examined by electronic microscopy. The relationship between the preparation method, morphology, and electrical conductivity was studied. Electronic microscopy images reveal that the nanocomposites exhibit well dispersed graphene platelets. The incorporation of EG to the PET results in a sharp insulator‐to‐conductor transition with a percolation threshold (?_c) as low as 0.05 wt %. An electrical conductivity of 10^?3 S/cm was achieved for 0.4 wt % of EG. The low percolation threshold and relatively high electrical conductivity are attributed to the high aspect ratio, large surface area, and uniform dispersion of the EG sheets in PET matrix. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Surface modification of silica nanoparticles by UV-induced graft polymerization of methyl methacrylate

In this study we modified the surface of silica nanoparticles with methyl methacrylate by UV-induced graft polymerization. It is a surface-initiated polymerization reaction induced by ultraviolet irradiation. The resulting organic-inorganic nanocomposites were near-monodisperse and fabricated without homopolymerization of the monomer. Substantial increase in mean particle size was observed by SEM image analysis after UV-induced grafting of methyl methacrylate onto pure silica particles. FT-Raman spectroscopy and X-ray photoelectron spectroscopy studies of these materials revealed the successful grafting of methyl methacrylate onto the silica surface. The formation of a covalent bond between the grafted PMMA chains and silica surface was indicated by FT-Raman spectra. Thermogravimetric analysis of the PMMA-grafted silica particles indicated the polymer contents in good agreement with SEM photographs.