Thermal and thermo‐oxidative stability of thermoplastic polymer nanocomposites with arylated [60]fullerene derivatives

Nanocomposite films of polystyrene (PS) and poly(methyl methacrylate) (PMMA) were prepared by loading four variations of fullerenes such as pristine C₆₀, multiarylated [60]fullerenes with tolyl (tolyl‐C₆₀) and phenol groups (phenol‐C₆₀), and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM). The TGA analysis showed no appreciable change in their thermal and thermo‐oxidative stabilities for PS/tolyl‐C₆₀ and PS/phenol‐C₆₀ films, but significant improvement up to +45°C for PS/C₆₀ and PS/PCBM films even under air. The thermo‐oxidative stability of PMMA/phenol‐C₆₀ and PMMA/PCBM, however, exhibited slightly larger improvements over that of PMMA/C₆₀. We believe that the radical‐scavenging ability of π‐conjugative fullerenes and the dispersibility of fullerene–polymer combinations play key roles in these enhancements. We also found that optimal loading occurred at a relatively low content of fullerenes (0.4–0.8 wt%) probably because larger amounts may interfere with the morphological interaction of polymer chains which is essential for the thermal persistency of polymer. POLYM. COMPOS. 37:1143–1151, 2016. © 2014 Society of Plastics Engineers     

Fullerene‐functionalized polycarbonate: Synthesis under microwave irradiation and nonlinear optical property

Fullerenation of polycarbonate (PC), a commercially important optical polymer, was achieved by direct reaction of C₆₀ and PC in the presence of azo‐bis‐isobutyronitrile (AIBN), using 1,1,2,2‐tetrachloroethane as the solvent under microwave irradiation (MI). Compared with conventional heating process, MI could significantly enhance the rate of the fullerenation under identical reaction conditions. The C₆₀ content of the fullerene‐functionalized polycarbonate (C₆₀‐PC) could be controlled via varying the C₆₀/PC feed ratio and the reaction time. The C₆₀‐PCs are soluble in common organic solvents such as THF and chloroform. The products were characterized by gel permeation chromatography, UV–vis, FTIR, TGA, DSC, ¹H NMR, and ¹³C NMR. The reaction of C₆₀ with PC under MI was monitored by electron spin resonance spectra, the fullerene radicals were detected in reaction solutions and also in the solid product polymers, indicating the radical mechanism of the reaction. The nonlinear optical property of C₆₀‐PCs in THF was investigated by the open‐aperture z‐scan technique at 527 nm, and its nonlinear absorption coefficient was found to be in the same order as that of C₆₀. POLYM. ENG. SCI., 46:399–405, 2006. © 2006 Society of Plastics Engineers     

New synthetic method for soluble starlike C60‐bonding polymers

Novel starlike C₆₀‐bonding polymers were synthesized by using the iniferter technique. The fullerene C₆₀ with pendent N,N‐diethyldithiocarbamate groups (C₆₀–SR) was used as polyfunctional photoiniferter. The effects of UV‐irradiation time and ambient temperature on the molecular weight of polymer were investigated. The photopolymerization with C₆₀–SR proceeded via a living‐radical mechanism, and gave soluble polyfunctional polymers (photoiniferters). Multiple polymer arms were attached to the C₆₀ core and the polymers obtained by C₆₀–SR could also be used as excellent crosslinking agents. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1286–1290, 2001     

Asymmetric and mikto-arm stars with a C60 core by grafting of macro-radicals or anionic polymer chains

Asymmetric and mikto-arm stars were synthesized by the stepwise addition of macro-radicals or of anionic polymer chains onto C₆₀. Pure di-adducts (PS_a)₂C₆₀ were obtained by atom transfer radical addition of a Br-terminated polystyrene (PS_aBr). Tetra-adducts (PS_a)₂C₆₀(PS_b)₂ and (PS_a)₂C₆₀(PI)₂ were prepared by grafting, respectively, two additional PS_bBr or PIBr onto (PS_a)₂C₆₀. The addition of ‘living’ polystyryllithium onto C₆₀ can be stoichiometrically controlled. For example, the reaction of four PS_aLi with one C₆₀ led to the formation of (PS_a)₄C₆₀⁴⁻(Li⁺)₄. The additional grafting of polystyryllithium (PS_bLi) or polyisoprenyllithium (PILi) provided, respectively, (PS_a)₄C₆₀(PS_b)₂ and (PS_a)₄C₆₀(PI)₂. All the stars were characterized using multiple detectors size exclusion chromatography (SEC).     

Synthesis and photophysical properties of a charm-bracelet type C60-grafted PPV derivative

Synthesis and photophysical properties of a new soluble C₆₀-grafted PPV polymer have been described. Fluorescence quenching of the PPV moiety in C₆₀-grafted PPV polymer was observed, suggesting the energy- and/or electron transfer within the polymer. The fluorescence decay profiles at around 500 nm of this polymer both in chloroform and benzonitrile display a single exponential decay giving the fluorescence lifetimes of 1.10-1.27 ns, which are slightly shorter than that of PPV (about 1.50 ns). The nanosecond transient absorption band of C₆₀-grafted PPV polymer was observed at 740 nm corresponded to the excited triplet state of C₆₀, which decreased in benzonitrile, indicating the existence of the extra decay path of the singlet excited state of the C₆₀ other than intersystem crossing. Upon heating this polymer exhibits typical semilunar liquid crystalline texture, being closely associated with its polymeric structure with long solubilizing alkoxy side chains.     

Synthesis and self-assembly in bulk of six-arm star-block copolymers with a C60 core

This study focuses on the synthesis and the structural characterization of various branched star-block copolymers (polyisoprene-block-polystyrene)₆C₆₀ with a fullerene C₆₀ as a core. Well defined 6-arm stars (PI-b-PS)₆C₆₀ with a low polydispersity and a precise control of the number of branches were prepared by grafting PI-b-PS diblock copolymers through the polystyrene block onto the C₆₀ core. The self-assembled structures formed in bulk were studied by Transmission Electron Microscopy (TEM) and Small Angle X-ray Scattering (SAXS) for both symmetric and asymmetric polystyrene-block-polyisoprene (PS-b-PI) diblock arms in the strong-segregation regime (65 ≤ χN ≤ 115). Various microstructures including lamellae, hexagonal packings of PS and PI cylinders as well as a gyroid phase were obtained by varying the volume fraction of polystyrene (f_PS) of the branches, leading to the formation of ordered, periodic and localized nanoscale dispersions of the C₆₀ in a polymer matrix including planes, threads and a 3D bicontinuous network of C₆₀.     

Synthesis and photoconducting properties of C60‐bonded polystyrene initiated with C60Cln

C₆₀‐bonded polystyrene was produced with a novel initiator system, C₆₀Cl_n/CuCl/2,2′‐bipyridine (where the average value of n is 20). The molar ratio of styrene/C₆₀Cl_n/CuCl/bpy was 100:1/20:1:2, and the polymerization temperature was 130°C. Gel permeation chromatography detected with an ultraviolet detector demonstrated that C₆₀ was chemically bonded to polystyrene. The linear increase in the number‐average molecular weight (by gel permeation chromatography) with the conversion indicated that this novel initiator system had some characteristics of living polymerization. A possible polymerization mechanism was examined. The photoconducting properties of C₆₀‐bonded polystyrene were better than those of polystyrene initiated with CCl₄. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3001–3004, 2002     

Polystyrene composites of single‐walled carbon nanotubes‐graft‐polystyrene

Single‐walled carbon nanotubes (SWCNTs) dispersed in N‐methylpyrrolidone (NMP) were functionalized by addition of polystyryl radicals from 2,2,6,6‐tetramethyl‐1‐piperidinyloxy‐ended polystyrene (SWCNT‐g‐PS). The amount of polystyrene grafted to the nanotubes was in the range 20‐25 wt% irrespective of polystyrene number‐average molecular weight ranging from 2270 to 49 500 g mol^?1. In Raman spectra the ratios of D‐band to G‐band intensity were similar for all of the polystyrene‐grafted samples and for the starting SWCNTs. Numerous near‐infrared electronic transitions of the SWCNTs were retained after polymer grafting. Transmission electron microscopy images showed bundles of SWCNT‐g‐PS of various diameters with some of the polystyrene clumped on the bundle surfaces. Composites of SWCNT‐g‐PS in a commercial‐grade polystyrene were prepared by precipitation of mixtures of the components from NMP into water, i.e. the coagulation method of preparation. Electrical conductivities of the composites were about 10^?15 S cm^?1 and showed no percolation threshold with increasing SWCNT content. The glass transition temperature (T_g) of the composites increased at low filler loadings and remained constant with further nanotube addition irrespective of the length and number of grafted polystyrene chains. The change of heat capacity (ΔC_p) at T_g decreased with increasing amount of SWCNT‐g‐PS of 2850 g mol^?1, but ΔC_p changed very little with the amount of SWCNT‐g‐PS of higher molecular weight. The expected monotonic decrease in ΔC_p coupled with the plateau behavior of T_g suggests there is a limit to the amount that T_g of the matrix polymer can increase with increasing amount of nanotube filler. Copyright © 2012 Society of Chemical Industry     

Interactions between fullerene(C60) and poly(ethylene oxide) in their complexes as revealed by high-resolution solid-state C NMR spectroscopy

A series of poly(ethylene oxide) (PEO)/fullerene(C₆₀) complexes are prepared by lyophilization. The intermolecular interaction and molecular motion in the complex are investigated by solid-state ¹³C NMR spectroscopy. An intense C₆₀ signal due to the intermolecular cross-polarization is observed in the ¹³C CP/MAS spectra of the complex samples, indicating a high degree of dispersion of C₆₀s in the complexes. By measuring the ¹³C spin-lattice relaxation times and ¹H transverse relaxation times of the complex sample and by comparing the static ¹³C spectrum of the pure C₆₀ sample with that of the complex sample, it is demonstrated that there exist n-π interactions between the n-orbitals of the PEO ether oxygen and the π-system of C₆₀. The C₆₀ molecules act as physical cross-links in the amorphous region of PEO, which greatly inhibit the mobility of the surrounding PEO chains, while the rapid isotropic rotation of C₆₀ molecules is also reduced to some extent due to the interactions with the polymer chains.     

Polyether-modified fullerenes

Summary Polyether-modified fullerenes have been prepared under mild conditions by reacting C₆₀ or C₇₀ in toluene with a precursor poly(oxyethylene) or poly(oxypropylene) polymer possessing amino end-groups. In the early stages of the interaction, soluble products are formed. Later, cross-linking proceeds between the polyfunctional fullerenes and the bifunctional polyethers. The non-crosslinked fullerene derivatives are soluble both in toluene and water; by evaporation of toluene, very adhesive films are formed.     

Convenient syntheses of fullerynes for ‘clicking’ into fullerene polymers

Alkyne-functionalized fullerenes (fullerynes) were designed and conveniently synthesized via Bingel reaction in one step with high yields. They were used to react with azido-functionalized polystyrene (PS) via Huisgen [3 + 2] cycloaddition ‘click’ chemistry to form two fullerene polymers: one with C₆₀ tethered to the end of a PS chain (C₆₀-1PS) and the other with C₆₀ tethered at the junction point of two PS chains of identical molecular weight (C₆₀-2PS). The fullerene polymers were characterized by ¹H NMR, ¹³C NMR, FT-IR, MALDI-TOF mass spectrometry and SEC. The results showed that the fullerene polymers are well-defined with narrow polydispersity and high fullerene functionality. Besides, aggregation of C₆₀ in THF was observed in the SEC traces. The optical properties of the fullerene polymers were studied by UV–Vis absorption spectroscopy, and the results suggested that the PS chain(s) on the fullerene core has no remarkable effect on the optic property of C₆₀. The thermal properties of the fullerene polymers were studied by TGA and DSC, and the results indicated that the two fullerene polymers with different C₆₀ content and distinct molecular topology may have different self-assemble architectures in the solid state. The well-defined fullerene polymers can be used as model compounds to study the self-assemble architecture of shape amphiphiles based on polymer-tethered molecular nanoparticles.     

Increase of photoluminescence from fullerene‐doped polymers under laser irradiation

Photoluminescence (PL) from fullerene (C₆₀ and C₇₀)‐doped polymers such as poly(methyl methacrylate) (PMMA), polystyrene (PS), poly(methyl phenyl silane) (PMPS) and poly(phenyl silsesquioxane) (PPSQ) increases gradually under laser irradiation in air (but not in vacuum and in nitrogen) and eventually becomes visible to the naked eye. Concomitantly, the PL peak is broadened and, in most cases, blue‐shifted. No such PL increases are observed for pure C₆₀ films made by vacuum vapor deposition and pure polymer films. Among the polymers used, fullerene‐doped PMMA has the greatest PL increase after several hours of laser irradiation and fullerene‐doped PMPS has the highest rate of PL increase at the initial stage of the laser irradiation. To gain an insight into the mechanism of the PL increase, laser‐irradiated fullerene‐doped PMMA samples were analyzed by UV‐Vis spectrophotometer, FT‐IR, mass spectrometry, GPC and NMR. The results show that the PL increase can be attributed to CH₆₀O_n‐polymer (or C₇₀O_n‐polymer) and oxidized fullerene‐polymer adducts formed by some laser‐induced photochemical reactions among fullerenes, oxygen and polymers.     

Formation and electrochemical properties of composites of the C60–Pd polymer and multi-wall carbon nanotubes

Preparation and electrochemical properties of a novel type of the composite made of multi-wall carbon nanotubes (MWCNTs) and two-component polymer of palladium and C₆₀ (C₆₀–Pd) were investigated using cyclic voltammetry, electrochemical impedance spectroscopy, and piezoelectric microgravimetry. A composite film was prepared by electrochemical deposition of C₆₀–Pd on the layer of MWCNTs immobilized on the electrode surface. The polymer forms islands of shells on the carbon multi-wall core. This composite is electrochemically active in the negative potential range due to the electroreduction of the fullerene moiety. In this potential range, specific pseudo-capacitance of the film of the MWCNT/C₆₀–Pd composite is 425 F g⁻¹ in the acetonitrile solution of tetra(n-butyl)ammonium perchlorate. The presence of MWCNTs makes the composite conductive also at potentials less negative than potentials of the C₆₀ electroreduction. The double-layer specific capacitance of this film is close to 15 F g⁻¹.     

Synthesis and photovoltaic properties of polythiophene derivatives with side chains containing C60 end group

A donor–acceptor double‐cable polythiophene derivative ( PT‐F1 ) with side chain containing C₆₀ end group was synthesized, and characterized by infrared, UV‐vis absorption and photoluminescence (PL) spectroscopy, and electrochemical cyclic voltammetry. Cyclic voltammogram of PT‐F1 shows the oxidation peak of the polymer main chains and the reduction peaks of the C₆₀ end groups, indicating that there is no interaction between the polymer main chains and side chain C₆₀ groups on the ground state. The UV‐vis absorption spectrum of PT‐F1 film is red‐shifted in comparison with that of its chloroform solution. The PL spectrum of the polymer main chain was quenched by the C₆₀ pendant on the side chain. Polymer solar cell with the structure of ITO/PEDOT:PSS/ PT‐F1 /Ca/Al was fabricated. The power conversion efficiency of the device based on PT‐F1 reached 0.274% under the illumination of AM 1.5, 100 mW/cm². © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Gas–liquid chromatographic study of polystyrene–n‐alkane interactions

Gas–liquid chromatography is used to study the thermodynamic interactions between polystyrene and n‐alkanes (C₆–C₁₀). Polystyrene is used as a stationary phase with n‐alkanes as the probe molecules. Retention times and specific retention volumes are measured over the temperature interval of 60 to 170°C. Partial molar free energy of mixing, polymer–solvent interaction parameter, glass‐transition temperature, and solubility parameter of polystyrene at infinite dilution are calculated. Experimental results are discussed in terms of the theoretical calculations and size of the probe molecules. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1291–1298, 2001     

Electrochemical properties of two-component polymers of palladium and pyrrolidine and piperazine derivatives of C60

Redox-active films have been generated via electrochemical reduction in a solution containing palladium(II) acetate and [C₆₀]fullerene, or derivatives of C₆₀. The C₆₀ derivatives include piperazine (piperazine-C₆₀), pyrrolidine (CH₃-pyr-C₆₀), and a pyrrolidine salt, [(CH₃)₂-pyr-C₆₀]⁺ attached to the fullerene unit. In these films, fullerene moieties are covalently bonded to palladium atoms to form a polymeric network. The polymer yields involving the piperazine and pyrrolidine derivatives of C₆₀ are significantly lower than the yield of the C₆₀/Pd film. The CH₃-pyr-C₆₀/Pd and [(CH₃)₂-pyr-C₆₀]⁺/Pd films are electrochemically active in the negative potential region due to the reduction of the fullerene moiety. Reduction of the CH₃-pyr-C₆₀/Pd film is accompanied by the transport of supporting electrolyte cations from the solution into the film. In the first reduction step of the [(CH₃)₂-pyr-C₆₀]⁺/Pd film, both cations and anions of the supporting electrolyte are involved. The piperazine-C₆₀/Pd film exhibits electrochemical activity at both negative and positive potentials. In the negative potential region, reduction of the fullerene cage takes place. Oxidation of the piperazine moiety is responsible for the observed current in the positive potential range. Here, the oxidation process of this polymer is significantly influenced by the presence of metallic palladium particles in the film.     

Fullerene polymer film as a highly efficient photocatalyst for selective solar fuel production from CO2

C₆₀-based polymeric systems have been constantly anticipated for sustainable solar energy conversion. Reported, herein is a C₆₀ polymer film as visible light active photocatalyst for efficient and selective reduction of CO₂ for the first time. The C₆₀ polymer photocatalyst is synthesized via covalent coupling of C₆₀ monomer units consisting of tetra substituted C₆₀-pyrene conjugates through spacer groups. The synthesized C₆₀ polymer photocatalyst possesses an extended network of well-defined repeating monomer units with good stability and visible light-induced photocatalytic activity. The enhanced visible light harvesting ability of C₆₀ polymer photocatalyst reasonably yields it with higher catalytic ability than its monomer unit. The C₆₀ polymer film photocatalyst upon coupling with the biocatalyst carries out highly selective visible light driven reduction of CO₂ to HCOOH (239.46 μmol). The tandem way of incorporating C₆₀ into visible light active polymeric films for continuous use may be highly rewarding for their extended photocatalytic activity for solar fuel production from CO₂. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48536.     

Synthesis of C60‐bonded polystyrene initiated with C60Cln/Ni(naph)2/P(Ph)3

A linear‐shaped polystyrene with C₆₀ core was prepared with a novel initiator system, C₆₀Cl_n (n average value is 20)/Ni(naph)₂/P(Ph)_3, and T_p was 130 °C. The results of gel‐permeation chromatography detected by UV detector and fluorescence spectrum of C₆₀‐PSt demonstrated that C₆₀ was chemically bonded to polystyrene. The linear increasing of molecular weights (M_n,GPC) with conversion indicated that this novel initiator system had some characters of living polymerization. A bathochromic shift was found in the UV–vis spectra curves with increasing concentration of C₆₀‐PSt in THF solution. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1215–1218, 2005     

A study on the concentration dependence of excimer formation in pyrenyl labelled polystyrene solutions

The fluorescence of pyrenyl labelled polystyrene has been investigated. The ratio of excimer to monomer intensities (I_e/I_m) is found to vary tortuously with increasing concentration (C) and displays two critical concentration points, C⁺ at about 3.2 × 10⁻² g ml⁻¹ and C_m at about 0.32 g ml⁻¹. In the region C⁺ < C < C_m, an abrupt increase of I_e/I_m is revealed because of intermolecular interaction. At C > C_m, the sharp decrease of I_e/I_m is ascribed to entanglements of polymer chains. © 1999 Society of Chemical Industry     

Electrochemistry of the films of a novel class C60 covalently linked PPV derivative: Electrochemical quartz crystal microbalance study in acetonitrile solutions of tetra‐n‐butylammonium cations

The electrochemical behaviors of a novel class C₆₀ covalently linked PPV derivatives (i.e., PPV‐1‐C₆₀ and PPV‐2‐C₆₀) in thin solid films as well as in solutions are reported. The first cathodic peak potentials of PPV‐1‐C₆₀ and PPV‐2‐C₆₀ have positive shifts by 30 and 50 mV, respectively, compared to pristine C₆₀ in formal cyclic voltammetry (CV). Simultaneous CV and piezoelectric microgravimetry of the drop‐coated thin solid films of PPV‐1‐C₆₀ and PPV‐2‐C₆₀ in acetonitrile solutions of TBA⁺ counteractions are strongly influenced by the structure of the polymer‐C₆₀, including the length of the chain macromolecule and the steric hindrance effect. In addition, the atomic force microscopy (AFM) images of PPV‐1‐C₆₀ and PPV‐2‐C₆₀ films deposited on Au/quartz electrode both exhibit even distribution. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2737–2741, 2002