Two‐stage copolycondensation of preformed oligomers with bisphenols by tosyl chloride/dimethylformamide/pyridine from distributions of resulting oligomers determined by a combination of gel permeation chromatography and NMR

A two‐stage co‐oligomerization of the oligomers initially formed from an equimolar mixture of isophthalic acid (IPA) and terephthalic acid (TPA) and 2,2‐bis(4‐hydroxyphenyl)propane (BPA, 50 mol %) with bisphenols (BPs, 20 mol %) was carried out using a tosyl chloride/dimethylformamide/pyridine condensing agent. The distributions of the resulting oligomers (n_x‐mers), which were quenched with methanol, were determined by a combination of gel permeation chromatography (GPC) and NMR. These distributions (presented by molar percentage) were conveniently calculated with the equation n_x (mol %) = n_x (% mol by GPC) × n₀ (mol % by NMR)/n₀ (% mol by GPC), where n_x (% mol) = n_x (wt % by GPC)/its molecular weight. The results showed the distributions of the preformed IPA/TPA‐BPA oligomers to be in fairly good accord with those obtained directly from GPC and to be supported by the NMR results. The calculation was applied to the co‐oligomers prepared up to a reaction of 0.7, at which there was an increase in the number of higher oligomers indivisible by GPC and the distributions could no longer be determined by molar percentage. The calculated distributions are discussed in relation to the results of copolycondensation. The sequence distributions in the resulting co‐oligomers, which were also examined by NMR, are compared with those in the copolymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 44–51, 2004     

Polyesterification of aromatic dicarboxylic acids and bisphenols with tosyl chloride/dimethylformamide/pyridine promoted by the improvement of the difficult solubility of the activated diacids with lithium chloride

The solution polyesterification of dicarboxylic acids in pyridine, the activated intermediates of which were difficult to dissolve in tosyl chloride/dimethylformamide/pyridine, was investigated in the presence of lithium chloride. The solubility of the activated dicarboxylic acids was largely improved by the presence of the salt, and the polycondensation with bisphenols was greatly facilitated. The salt was more effectively added to a pyridine solution of dicarboxylic acids than to the activated dicarboxylic acids in pyridine. The favorable additive effect on the improved solubility was attributed to a lowered degree of association of the activated dicarboxylic acids, which led to distributions of the resulting oligomers from bisphenols at an earlier stage closer to the theoretical ones and yielded better polycondensation results. The reaction, which proceeded through favorable distributions of the co‐oligomers, produced copolymers of higher inherent viscosities and slightly block sequence distributions determined by NMR. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2725–2733, 2004     

Hybrid organosilazane/organosilylamine telechelic oligomers—I. Two-dimensional NMR spectroscopy characterization of dimethylsilylethylenediamine oligomers

The detailed characterization of multifunctional hybrid organosilazane/organosilylamine telechelic oligomers by IR and ¹H, ¹³C and ²⁹Si NMR spectroscopy in one and two dimenions has been undertaken. The specific multifunctional oligomers, comprising NH/NH₂ or SiCl functionalities depending on the monomer feed-ratio, were prepared from mono- and di-functionally reacted dichlorodimethylsilane (DDS) and mono-, di-, tri- and tetra-functionally reacted ethylenediamine (EDA). Varying the feed-ratio afforded control of the microstructures of the oligomers and the preparation of oligomers with, in some cases, conterminously located silicon–chlorine (SiCl) groups. The combination of the NMR methods with the IR technique has enabled the detailed microstructural characterization of the oligomers and the identification of the functionalities therein. This approach and the knowledge gained from the DDS/EDA system has been applied to the microstructural characterization of other hybrid organosilazane/silylamine preceramic telechelic oligomers.     

Luminescent copolymers for applications in multicolor‐light‐emitting devices

Light‐emitting diodes based on organic materials [organic light‐emitting diodes (OLEDs)] have attracted much interest over the past decade. Several different attempts have been made to realize multicolor OLEDs. This article describes a new approach based on energy transfer in a donor/acceptor system. A copolymer containing both donor and acceptor compounds as comonomer units is prepared. The polymer consists of a derivative of a luminescent dye [4‐dicyanmethylene‐2‐methyl‐6‐4H‐pyran (DCM); acceptor compound], which is copolymerized with fluorene (donor compound) to combine the properties of an electroactive polymer with a highly luminescent dye. Photochemical processing is achieved by UV irradiation of this copolymer in the presence of gaseous trialkylsilanes. This reagent selectively saturates the C?C bonds in the DCM comonomer units while leaving the fluorene units essentially unaffected. As a result of the photochemical process, the red electroluminescence of the acceptor compound vanishes, and the blue‐green electroluminescence from the polyfluorene units is recovered. Compared with previous approaches based on polymer blends, this copolymer approach avoids problems associated with phase‐separation phenomena in the active layer of OLEDs. © 2006Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4317–4327, 2006     

Synthesis of Molecular Wires of Linear and Branched Bis(terpyridine)‐Complex Oligomers and Electrochemical Observation of Through‐Bond Redox Conduction

Films of linear and branched oligomer wires of Fe(tpy)₂ (tpy=2,2′:6′,2′′‐terpyridine) were constructed on a gold‐electrode surface by the interfacial stepwise coordination method, in which a surface‐anchoring ligand, (tpy? C₆H₄N?NC₆H₄? S)₂ ( 1 ), two bridging ligands, 1,4‐(tpy)₂C₆H₄ ( 3 ) and 1,3,5‐(C?C? tpy)₃C₆H₃ ( 4 ), and metal ions were used. The quantitative complexation of the ligands and Fe^II ions was monitored by electrochemical measurements in up to eight complexation cycles for linear oligomers of 3 and in up to four cycles for branched oligomers of 4 . STM observation of branched oligomers at low surface coverage showed an even distribution of nanodots of uniform size and shape, which suggests the quantitative formation of dendritic structures. The electron‐transport mechanism and kinetics for the redox reaction of the films of linear and branched oligomer wires were analyzed by potential‐step chronoamperometry (PSCA). The unique current‐versus‐time behavior observed under all conditions indicates that electron conduction occurs not by diffusional motion but by successive electron hopping between neighboring redox sites within a molecular wire. Redox conduction in a single molecular wire in a redox‐polymer film has not been reported previously. The analysis provided the rate constant for electron transfer between the electrode and the nearest redox‐complex moiety, k₁ (s^?1), as well as that for intrawire electron transfer between neighboring redox‐complex moieties, k₂ (cm² mol^?1 s^?1). The strong effect of the electrolyte concentration on both k₁ and k₂ indicates that the counterion motion limits the electron‐hopping rate at lower electrolyte concentrations. Analysis of the dependence of k₁ and k₂ on the potential gave intrinsic kinetic parameters without overpotential effects: k₁⁰=110 s^?1, k₂⁰=2.6×10¹² cm² mol^?1 s^?1 for [n Fe 3 ], and k₁⁰=100 s^?1, k₂⁰=4.1×10¹¹ cm² mol^?1 s^?1 for [n Fe 4 ] (n=number of complexation cycles).     

Electronic spectral and photophysical properties of some p-phenylenevinylene oligomers in solution and thin films

A comprehensive photophysical and spectroscopic study of a new class of p-phenylenevinylene oligomers (PPV-trimers) possessing different alkyl and alkyloxy sidechain substituents and different end groups (aldehyde, CC, phenylene and anthracene units) was undertaken in solution at room temperature (293 K), low temperature (77 K) and in thin films. The study comprises absorption, emission and triplet–triplet absorption spectra, together with quantitative measurements of quantum yields (fluorescence, intersystem crossing, internal conversion and singlet oxygen formation) and lifetimes. The data allow the determination of rate constants for all decay processes. From these, several conclusions could be drawn. Changing from alkyl to alkyloxy substituents does not change fluorescence and internal conversion yields but decreases the (already small) intersystem crossing yield. The introduction of anthracene at the terminal ends of the PPV-trimers leads to the lowest fluorescence yield reported in this study. Of particular importance is the fact that the fluorescence quantum yields in films are of the same order of magnitude as those in solution, which suggests the potential for use of these oligomers for light-emitting device applications. With one of the alkyloxy derivatives, a more detailed study of the early part of the fluorescence decay was made, and it was found that upon excitation a fast conformational relaxation process of the initially excited oligomer occurs, leading to a more planar conjugation segment.     

Effect of monomer molecular flow on electrode surface on the structure of poly(α-tetrathiophene) obtained by anodic polymerization

Different structures have been found for poly(α-tetrathiophene) [poly(α-4TF)] electrosynthesized on Pt by anodic oxidation of 1.0 mM monomer solutions in media such as 45:35:20 (v/v/v) acetonitrile/THF/DMF, 45:35:20 (v/v/v) acetonitrile/ethanol/DMF and 72:28 (v/v) acetonitrile/DMF containing 0.1 M LiClO₄; as well as 72:28 (v/v) acetonitrile/DMF with 0.1 M NaClO₃, under dynamic and static conditions at 25 °C. In all cases the polymer was generated by chronoamperometry at 1.000 V vs. Ag∣AgCl, corresponding to the first oxidation peak detected by cyclic voltammetry. Uniform, adherent, insoluble and black polymer films were obtained under these conditions. The resulting structures have been elucidated by combining the information of their IR spectrum, n_ox-value and doping level of the counterion. The degree of crosslinking of every polymer has been quantified and related to the molecular flow of monomer on the Pt electrode. A monomer concentration flow between 4 × 10⁻⁶ and 5 × 10⁻⁶ mmol cm⁻² s⁻¹ was determined as the limiting value below which the polymer grows with crosslinking. This value corresponds to the electropolymerization rate of α-4TF by Pt area unit at 25 °C.     

Photoinduced self-substitution of haloquinones

A series of novel oligo(halobenzoquinoid) compounds have been obtained from the photoinduced self-substitution of 2,5-dibromo-1,4-benzoquinone (1a), 2,6-dibromo-1,4-benzoquinone (1b), 2-chloro-1,4-benzoquinone (1c), 2-bromo-5-chloro-1,4-benzoquinone (1d), 2,3,5,6-tetrachloro-1,4-benzoquinone (1e) and 1,4-benzoquinone (1f) in the presence of N,N-dimethyl-t-butylamine (2) in acetonitrile. Dimers, trimers and/or pentamers of these haloquinones were found to be the major products.     

A novel hyperbranched polyester acrylate used for microfabrications

A novel hyperbranched polyester acrylate (HPEA) was synthesized based upon ethylenediamine tetraacetic acid as a “core” molecule, 5‐hydroxyisophthalic acid as an AB₂ monomer, and 2‐hydroxyethyl acrylate as an endcapping reagent. The obtained oligomer has an unsaturation concentration of 4.10 mmol_C?C g^?1 measured by nuclear magnetic resonance and a wide molecular weight distribution of 1.64 measured by gel permeation chromatography. The two‐photon absorption (TPA) photopolymerization of HPEA under the exposure of a Ti : sapphire femtosecond laser with a wavelength of 800 nm was investigated through laser exposure dose‐dependant spatial resolutions of its resins. The TPA photopolymerization thresholds at the range 1.6–4.3 × 10⁷ mJ cm^?2, and exposure dose windows at the range 3.4–4.3 for three formulations were determined. A spatial resolution of 0.85 μm was obtained through the TPA photopolymerization of the formulation containing 1 wt% photoinitiator and 0.3 wt% photoinhibitor. A diffraction grating and real three‐dimensional coupled gear wheel created by TPA photopolymerization were described to demonstrate the unique capability of HPEA in microfabrications. Copyright © 2004 John Wiley & Sons, Ltd.     

Ring-opening metathesis polymerization (ROMP) of isomerically pure functional monomers and acyclic diene metathesis depolymerization (retro-ADMET) of functionalized polyalkenamers

ROMP and retro-acyclic diene metathesis (ADMET) were used for the synthesis of new functional polymers and functional oligomers, respectively. Purely exo and enantiomerically pure norbornene and 7-oxanorbornene derivatives were prepared using stereospecific synthesis, effective fractionation and high yield condensation reactions. Successful ROMPs of those monomers were performed using either the new carbenic Schrock’s or Grubb’s catalysts or in some cases a classical bicomponent catalyst. New functional polymers such as optically active poly(norbornene-2-carboxylic acid), reactive poly(norbornene-2-azlactone), and side-chain liquid crystal polyoxanorbornenes were fully characterized. On the other hand, successful depolymerizations of 1,4-polyisoprene and of epoxidized 1,4-polybutadiene via cross-metathesis with 4-octene were performed using a stabilized bicomponent catalyst and the Grubb’s catalyst, respectively. Conditions for the controlled synthesis of epoxidized oligobutadienes and of epoxydienic monomers via retro-ADMET were clearly defined.