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1.
A series of novel fluorinated alicyclic-functionalized polyimides (FPI-x) were prepared from a new alicyclic-functionalized diamine, 1,3-bis ((4-amino-2-(trifluoromethyl)phenoxylmethylene)-1,2,2-trimethyl cyclopentane (BAFMT), which was derivated from natural-(D)-camphor via multi-step process. The influence of the presence of the alicyclic and fluorinated structure on the general properties of the polymers was systematically investigated in terms of optical, thermal and mechanical properties, solubility and hydrophobicity, rendering the general structure–properties relationships for the FPI-x. Compared with the analogous control aromatic polyimide NPI-x, FPI-x shows better solubility, improved optical transparency, lower moisture absorption and surface energy, owing to the presence of the fluorine-containing group and alicyclic structure in the polymer chain. Although presenting a slight decrease as compared with NPI-x, the good thermal stability of polyimide was retained on the large in the fluorinated alicyclic-functionalized polymer FPI-x, with Tg ranging in 197–233 °C and Td5 ranging in 374–420 °C. A particular research emphasis were placed on employing the dielectric relaxation technique to study the dielectric constant (ε′), dielectric loss (ε″) and electric modulus (M″) of the fluorinated alicyclic-functionalized polyimide film FPI-4 and its control sample NPI-4. The observed dielectric relaxations have been fully studied by integrating the contributions of the specific structure and functional groups. It is revealed that the presence of fluorinated alicyclic-functionalized group endows FPI-4 with lower dielectric constant ε′ (2.88 at 1 MHz and 25 °C) and dielectric loss ε″ (0.0058 at 1 Hz and 25 °C) than NPI-4 (3.49 and 0.0084) and commercial Kapton HN (3.19 and 0.006) with the same measurement frequency and temperature. 相似文献
2.
Yun-Hi Kim 《Polymer》2005,46(13):4647-4653
New poly(terphenylenevinylene) derivative with an alkoxy group and an electron withdrawing cyano group, poly(1,4-phenylene-2′-methoxy-5′-ethylhexyl-1′,4′-phenylene-1″,4″-phenylene-α-cyanovinylene), was synthesized via the Suzuki coupling reaction. The polymer was completely soluble in common organic solvent and showed good thermal stability up to 380 °C. The presence of the electron withdrawing cyano group lowered LUMO energy level and the presence of the electron donating alkoxy group increased HOMO energy level of the polymer relative to those of poly(terphenylenevinylene). Light emitting diodes (LEDs) with the configuration ITO/PTPCNV/Al and ITO/PPV/PTPCNV/Al were fabricated. ITO/PTPCNV/Al device showed turn on voltage of 5 V (0.005 mA), however, ITO/PPV/PTPCNV/Al exhibited turn on voltage of 2.5 V (0.003 mA). The maximum brightness of the ITO/PPV/PTPCNV/Al device is about 5200 cd/m2 at 8 V with a maximum efficiency of 1.243 lm/W. The EL spectrum of the ITO/PPV/PTPCNV/Al device, which was consistent with PL spectrum of PTPCNV, had a maximum peak at 491 nm with a shoulder peak at around 520 nm. 相似文献
3.
Yanzhe Wu Amy M. Ballantyne Dezhi Zhou Geoffrey M. Spinks David Officer Gordon G. Wallace 《Electrochimica acta》2007,53(4):1830-1836
A solution-processable polythiophene, poly((E)-4,4″-didecoxy-3′-styryl[2,2′:5′,2′′]terthiophene) demonstrated large electrochemically induced strain up to 11.5%. Free-standing polymer films were characterised using four-point probe conductivity measurements, cyclic voltammetry and electrochemical actuation measurements. Conductivities of ∼6 × 10−5 S/cm (reduced state) or ∼1-2 S/cm (oxidised state) were measured. Well-defined polymer oxidation-reduction responses were observed in both the propylene carbonate and acetonitrile electrolytes, with electrochemical efficiency of >80% observed under ideal conditions. Results obtained suggested that the actuation strain approximately correlates with the size of the anion (i.e. TFSI > PF6− > ClO4−) used in the electrolyte. The largest strain ∼11.5% was obtained in an electrolyte solution consisting of 0.1 M Li.TFSI in acetonitrile. The maximum strain attainable increased with an increase in the anodic potential applied and decreased with an increase in stimulation frequency or increasing mechanical load. Such functionalised polythiophene material has the combined advantage of solution processability and the ability to produce large strain. 相似文献
4.
M. Krompiec I. Grudzka M. Filapek ?. Skórka S. Krompiec M. ?apkowski M. Kania W. Danikiewicz 《Electrochimica acta》2011,(24):8108
A bis-bithiophenyl derivative of diquat, 3,10-bis(2,2′-bithiophene-5-yl)-6,7-dihydropyrido[1,2-a:2′,1′-c]pyrazinodiynium hexafluorophosphate (bt2dq), was synthesized by quaternization of 5,5″-bis(2,2′-bithiophene-5-yl)-2,2′-bipyridine with 1,2-dibromoethane. Its UV–vis absorption spectrum is explained by TD-DFT calculations. It shows the electrochemical properties characteristic for bipyridinium salts (viologens and diquats) and can be electropolymerized to form a conjugated polymer composed of alternating quaterthiophene and diquat blocks. The polymer has been characterised by cyclic voltammetry and UV–vis spectroelectrochemistry: it can be reversibly oxidized, with spectral signs of p-doping of the oligothiophene blocks, and reversibly reduced, with formation of viologen-like cation radicals, which dimerize or form π-stacks. 相似文献
5.
J ChenA.K Burrell G.E CollisD.L Officer G.F SwiegersC.O Too G.G Wallace 《Electrochimica acta》2002,47(17):2715-2724
Novel ferrocene-substituted thiophene and terthiophene compounds, trans-1-(3′-thienyl)-2-(ferrocenyl)ethene and trans-1-((2′,2″:5″,2?-terthiophen)-3″-yl)-2-(ferrocenyl)ethene, have been used to produce homopolymer and copolymer materials. The copolymer of trans-1-(3′-thienyl)-2-(ferrocenyl)ethene with pyrrole and the homopolymer of trans-1-((2′,2″:5″,2?-terthiophen)-3″-yl)-2-(ferrocenyl)ethene were characterised using cyclic voltammetry (CV), UV-visible spectroscopy, scanning electron microscopy (SEM) and four point probe conductivity measurements. Results obtained suggest that the ferrocene moiety plays a catalytic role in the electropolymerisation process. Both the copolymer and homopolymer displayed cyclic voltammograms with redox peaks that can be assigned to the ferrocene moiety and the polymer backbone. The UV-visible spectra and morphology of the copolymer of trans-1-(3′-thienyl)-2-(ferrocenyl)ethene with pyrrole were similar to those of polypyrrole, but the spectra and morphology of the homopolymer of trans-1-((2′,2″:5″,2?-terthiophen)-3″-yl)-2-(ferrocenyl)ethene were different from those of polyterthiophene. The conductivity of the copolymer was determined to be 0.13 S cm−1 whereas that of the homopolymer of trans-1-((2′,2″:5″,2?-terthiophen)-3″-yl)-2-(ferrocenyl)ethene was 82.6 μS cm−1. The copolymer or homopolymer modified Pt disk electrodes facilitated access to the redox centre within Cytochrome C during CV, and their potential use as biosensors has been demonstrated. 相似文献
6.
Fevzi Ç. Cebeci 《Electrochimica acta》2007,52(5):2158-2165
The synthesis and characterization of a novel donor acceptor donor type bis(3,4-ethylene-dioxythiophene)-(4,4′-dinonyl-2,2′-bithiazole) comonomer and its electrochemically prepared polymer on carbon fiber, Pt button and ITO plate is reported in this paper. Cyclic voltammetry of the polymer in 0.1 M Et4NBF4/CH2Cl2 exhibits a very well defined and reversible redox processes and this co-monomer can be either p-doped or n-doped. The half-wave oxidation potentials of the polymer (E1/2) were observed at 0.303 and 0.814 V versus Ag/AgCl. The polymer is electrochromic; the onset for the π-π* transition (Eg) of 1.75 eV with a λmax at 2.15 eV and the homogeneous and high quality film of the polymer is stable of its optical properties offering fast switching time which is less than 0.25 s. The morphological studies reveal that the polymer was deposited as a continuous and very well adhering film to surface of the carbon fiber microelectrode. All these properties make this polymer favorable for use in electronic devices. 相似文献
7.
Three novel electroactive copolymers, consisting of alternating naphthalene bisimide and oligoarylene segments have been synthesized and studied by cyclic voltammetry and UV–vis-NIR spectroelectrochemistry. These studies show that the conjugation between both copolymer segments is very weak and the reduction of the bisimide part is essentially uninfluenced by the oligoarylene segment. The oxidation of the oligoarylene segment strongly depends on its length but is not affected by the presence of the bisimide part. The HOMO levels, determined electrochemically are systematically below −5.0 eV with respect to the vacuum level, changing from −5.45 eV for poly[1,4-phenylene-(4,3′(4′),3″-trioctyl-2,2′,5′,2″-terthiophene-5,5″-diyl)-1,4-phenylene-1,4,5,8-naphthalenediimide-N,N′-diyl] (6) to −5.50 eV in poly[1,4-phenylene-(4,4′-dioctyl-2,2′-bithiophene-5,5′-diyl)-1,4-phenylene-1,4,5,8-naphthalenediimide-N,N′-diyl] (5) and −5.84 eV for poly[1,4-phenylene-(3,4-dioctylthiophene-2,5-diyl)-1,4-phenylene-1,4,5,8-naphthalenediimide-N,N′-diyl] (4). The LUMO levels in all three cases are close to −4.0 eV. The obtained results clearly indicate that 5 and 6 are good candidates for the fabrication of ambipolar transistors operating in air whereas 4 can be considered as an active component of n-channels FETs. 相似文献
8.
A simple method was developed for the preparation of [Ru(bpy)2tatp]2+-based aggregates (where bpy = 2,2′-bipyridine, tatp = 1,4,8,9-tetra-aza-triphenylene) on an indium tin oxide (ITO) electrode in the presence of DNA-stabilized single-walled carbon nanotubes (DNA–SWCNTs). The presence of SWCNTs in the concentration range from 0.02 to 0.125 g L−1 dispersed with 0.25 mmol L−1 DNA was found to promote the immobilization of [Ru(bpy)2tatp]2+ on the ITO electrode by the method of repetitive voltammetric sweeping. The photoluminescence of [Ru(bpy)2tatp]2+ incorporating DNA–SWCNTs both in solution and on the ITO electrode was systematically investigated by emission spectra and fluorescence microscopic imaging. An excess amount of SWCNTs can quench the photoluminescence of [Ru(bpy)2tatp]2+ enhanced by DNA. The anodic potentials combined with CW green laser via an optical microscope was found to significantly increase the emission intensity of [Ru(bpy)2tatp]2+–DNA–SWCNTs aggregates on the ITO electrode. In addition, the electrochemical fabrication and photoluminescence principles of [Ru(bpy)2tatp]2+–DNA–SWCNTs aggregates on the ITO electrode tuned by the external electric fields were discussed in detail. 相似文献
9.
Water-soluble sulfonated poly(diphenylamine) (SPDPA) was synthesized and applied as a hole injection layer (HIL). It was characterized in terms of 1H NMR, 13C NMR, elemental analysis (EA), UV-vis, Raman, ultraviolet photoelectron spectroscopies (UPS) and TGA thermal stability measurement. The high transparency in visible region and acceptable conductivity were beneficial as HIL material. The topographic image obtained from Atomic Force Microscope shows that the surface of SPDPA-coated indium tin oxide (ITO) is smoother than that of bare ITO. Raman spectra indicate that SPDPA possesses the higher oxidation and doping level due to SO3H group on the phenyl ring, rendering SPDPA the higher work function with 0.35 eV than PDPA from UPS spectra. The electroluminescence efficiency of polymer light emitting diode using poly(2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylene vinylene) (MEH-PPV) as an active layer and SPDPA as HIL can be reached 2.0 cd/A, showing the slightly better performance than that using PEDOT:PSS as HIL. 相似文献
10.
The chiral polymer P-1 incorporating (S)-2,2′-binaphthol (BINOL) and (S)-2,2′-binaphthyldiamine (BINAM) moieties in the main chain of the polymer backbone was synthesized by the polymerization of (S)-6,6′-dibutyl-3,3′-diformyl-2,2′-binaphthol (S-M-1) with (S)-2,2′-binaphthyldiamine (S-M-2) via nucleophilic addition-elimination reaction, and the chiral polymer P-2 could be obtained by the reduction reaction of P-1 with NaBH4. The fluorescence intensity of the chiral polymer P-1 exhibits gradual enhancement upon addition of (d)- or (l)-phenylalaninol and keeps nearly a linear correlation with the concentration molar ratios of (d)- or (l)-phenylalaninol. The value of enantiomeric fluorescence difference ratio (ef) is 6.85 for the chiral polymer on (d)-phenylalaninol. On the contrary, the chiral polymer P-2 shows no obvious fluorescence response toward either (d)- or (l)-phenylalaninol. 相似文献
11.
Chiara Zanardi Roberta Scanu Laura Pigani Maria I. Pilo Gavino Sanna Renato Seeber Nadia Spano Fabio Terzi Antonio Zucca 《Electrochimica acta》2006,51(23):4859-4864
A new terthienyl derivative, 4′-[(2,2′:5′,2″-terthien-3′-yl)methoxy]-2,2′:6′,2″-terpyridine, was synthesised in order to electrogenerate a new conducting polymer as an electrode coating suitable to complex metal ions. The characteristics of the system obtained have been defined through electrochemical and spectroelectrochemical techniques. The physical and chemical properties of 4′-[(2,2′:5′,2″-terthien-3′-yl)methoxy]-2,2′:6′,2″-terpyridine are compared with those of 3′-hydroxymethyl-2,2′:5′,2″-terthiophene, i.e. the corresponding trimer not bearing the terpyridine ligand. Under the same conditions for both monomers, both electrochemical and spectroelectrochemical tests show that 4′-[(2,2′:5′,2″-terthien-3′-yl)methoxy]-2,2′:6′,2″-terpyridine leads to the formation of a narrower molecular weight distribution, with shorter-conjugated polymer chains. 相似文献
12.
A copolymer of anti-5,15-bis([2′,2″:5″,2″′-terthiophene]-3″-yl)-2,8,12,18-tetra-n-butyl-3,7,13,17-tetramethylporphyrin (1) with 2,2′:5′2″-terthiophene (2) was successfully electrosynthesised and was then characterised by cyclic voltammetry, UV-Vis spectroscopy, four-point probe conductivity measurement, and scanning electron microscopy. This novel light harvesting conducting copolymer was then incorporated into photoelectrochemical cells using a liquid electrolyte and tested for photovoltaic responses. The effect of zinc incorporation into the porphyrin cavity was also investigated, and the best device generated an open circuit voltage of 185 mV, short circuit current of 881 μA cm−2 with a fill factor of 0.36 and energy conversion efficiency of 0.12% under a halogen white light intensity of 500 W m−2. 相似文献
13.
The synthesis of a new functionalized terthiophene monomer with an unsaturated side chain, 3-((2′:2″,5″:2?-terthiophene)-3″-yl) acrylic acid, is described. A conducting polymer was obtained by electropolymerization of the functionalized monomer. The properties of the polymer were investigated using FT-IR, Raman and UV-vis spectroscopy. The application of the polymer as an active substrate for a genosensor is demonstrated by the covalent attachment of amino-end modified oligonucleotide probes to the carboxylic acid group of the polymer. The hybridization of the complementary ODNs can be clearly detected by an increase in the admittance without the need for an indicator or any sample modifications. 相似文献
14.
Optimised matrix-assisted laser desorption/ionisation (MALDI) and electrospray ionisation (ESI) mass spectrometry (MS) methodologies were systematically compared in terms of their relative abilities to identify distinct chemical species present in samples associated with a polymer mechanistic study. In order to perform the investigation, formation processes involved in atom transfer radical polymerisation (ATRP) mediated methyl acrylate (MA) star polymerisations were studied. In addition to the 4-armed ATRP initiator employed in the polymerisations, initiator side-products were found to generate oligomeric chains. At a relatively high monomer to polymer conversion, terminal Br loss was observed in these oligomers; this Br loss was hypothesised to occur via degradative transfer reactions involving the radicals (CH3)2?OH, ?H3 and ?H2COCH3, which were derived from the acetone used as a solvent in the polymerisations, as well as hydrogen radicals donated by the ligand N,N′,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA). In performing these studies, ESI was found to identify a greater number of distinct chemical species in the samples under investigation when compared to the employed MALDI technique, suggesting that the utilisation of ESI must be strongly considered in polymer mechanistic investigations if the maximum number of end-group functionalities within a given polymer sample are to be identified. 相似文献
15.
The oxidative coupling polymerization of racemic-, (R)-, and (S)-2,2′,3,3′-tetrahydroxy-1,1′-binaphthyl derivatives bearing a crown ether moiety was carried out in the presence of a Cu(I) or Cu(II) catalyst with various ligands, such as N,N,N′,N′-tetramethylethylenediamine, (S)-(+)-1-(2-pyrrolidinylmethyl)pyrrolidine, (−)-sparteine [(−)Sp], and (S)-(−)-2,2′-isopropylidenebis(4-phenyl-2-oxazoline). Methanol-insoluble poly(binaphthyl crown ether) with a molecular weight up to Mn=4.1×103 was synthesized in moderate yields. Polymerization using (−)Sp proceeded in an S-selective manner; the polymer with the highest negative specific rotation was obtained with the (S)-monomer. The obtained polymers exhibited characteristic abilities for chiral recognition toward amino acids, such as 2-phenylglycine hydrochloride and 2-phenylglycine methyl ester hydrochloride. 相似文献
16.
A novel conjugated alternating copolymer (PCzDBSe) based on N-9′-heptadecanyl-2,7-carbazole and 5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzoselenadiazole) was synthesized by Suzuki polycondensation. The polymer reveals excellent thermal stabilities with the decomposition temperature (5% weight loss) of 390 °C and the glass-transition temperature of 140 °C. The absorption peaks of the polymer are located at 412 and 626 nm, respectively, while the absorption onset is extended to 716 nm, which is 56 nm red-shifted as compared with its analogue, poly[N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT). The HOMO and LUMO levels of the polymer were estimated to be −5.28 and −3.55 eV, respectively, with an optical bandgap of 1.73 eV. The hole mobility of PCzDBSe as deduced from a solution-processed organic field effect transistor (OFET) was found to be 3.9 × 10−4 cm2 V−1 s−1. Polymer solar cells (PSCs) based on the blends of PCzDBSe and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) with a weight ratio of 1:4 were fabricated. Under AM 1.5 (AM, air mass), 100 mW cm−2 illumination, the devices were found to have an open-circuit (Voc) of 0.75 V, a short-circuit current density (Jsc) of 7.23 mA cm−2, a fill factor (FF) of 45% and a power conversion efficiency (PCE) of 2.58%. The primary results indicate that 5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzoselenadiazole) is a promising unit for low bandgap polymer for polymer solar cells. 相似文献
17.
In this study, the effects of TiO2 addition on the physical and photoelectrochemical properties of ZnO thin films have been investigated. The (TiO2)x–(ZnO)1−x nanocomposite thin films were dip-coated on both glass and indium tin oxide (ITO)-coated conducting glass substrates with various values of x, specifically 0, 0.05, 0.1, 0.25 and 0.5. Optical properties of the samples were studied by UV–vis spectrophotometry in the range of 300–1100 nm. The optical spectra of the nanocomposite thin films showed high transparency in the visible region. The optical bandgap energy of the (TiO2)x–(ZnO)1−x films increased slightly with increasing values of x. The crystalline structure of the nanocomposite films was investigated by X-ray diffraction, which indicated the formation of ZnO nanocrystals in the thin films with x < 0.5. Moreover, the crystallinity of the films decreased with increasing values of x. The surface chemical composition of the samples was investigated by X-ray photoelectron spectroscopy (XPS), which revealed stoichiometric ZnO and TiO2 on the surfaces of the films. The photoelectrochemical properties of the samples were also characterized using a high-pressure xenon light source and KOH electrolyte. The addition of 10 mol% (x = 0.1) TiO2 to the ZnO thin films resulted in the best photoresponse in the visible region of the solar spectrum. In addition, the effect of TiO2 concentration on the electrical properties and the flat-band potential of the (TiO2)x–(ZnO)1−x system was studied by impedance spectroscopy; x = 0.1 exhibited the highest donor density and charge-transfer resistance. 相似文献
18.
Direct anodic oxidation of (S)-(−)-1,1′-bi-2-naphthol dimethyl ether (BNME) in CH2Cl2/CHCl3 containing boron trifluoride diethyl etherate (BFEE) as the supporting electrolyte led to facile electrodeposition of high-quality free-standing poly((S)-(−)-1,1′-bi-2-naphthol dimethyl ether) (PBNME) film on stainless steel (SS)/indium tin oxide (ITO) electrodes. As-formed PBNME films showed good electroactivity and redox stability in CH2Cl2-BFEE, BFEE, and even in concentrated sulfuric acid. Both doped and dedoped PBNME films were partly soluble in strong polar solvents, such as dimethyl sulfoxide (DMSO). Quantum chemistry calculations of BNME and FT-IR spectrum of dedoped PBNME films demonstrated that the polymerization probably occurred at 4- and 4′-positions. Optical rotation determination showed that the conformation of the monomer was maintained during the electrochemical polymerization process and the polymer exhibited greatly enhanced optical rotation value with main chain axial chirality compared with that of the monomer. Fluorescent spectral studies indicated that soluble PBNME was a good blue-light emitter with maximum emission at 415 nm and fluorescence quantum yield of 0.15, while solid-state PBNME film showed its emission centered at 380 nm. Furthermore, as-formed PBNME manifested favorable thermal stability and relatively high electrical conductivity of about 10−1 S cm−1 at room temperature. 相似文献
19.
Brent Hilker 《Polymer》2010,51(21):4790-4805
Poly(methyl methacrylate) (PMMA) composites were made from a polar metalloporphyrin [5-(4′,4′,5′,5′-tetramethyl[1′,3′,2′]dioxaborolan-2′-yl)-10,20-diphenylporphyrinato]zinc(II) (Zn(II)Bpin-DPP) in select weight % (wt%). Differential Scanning Calorimetry (DSC) showed that porphyrin acted as an antiplasticizer raising the glass transition (Tg) from 105 °C to 123 °C. Dielectric Analysis (DEA) was performed in the frequency range of 0.3 Hz to 100 kHz between −150 and 270 °C. Permittivity (?′), loss factor (?″) and dielectric response of beta (β), alpha beta (αβ), and conductivity relaxations were studied. Previous DEA data was limited to 190 °C. This study brings analysis to 270 °C which is start point for the first part of PMMA degradation. Thus forwarding DEA can be used to evaluate PMMA degradation. The electric modulus formalism is used to reveal the β and conductivity relaxations. The apparent activation energies (Ea) for the molecular relaxations are presented. AC (σAC) and DC (σDC) conductivity are also evaluated. 相似文献