The synthesis of high conductivity poly(3,4‐ethylenedioxythiophene) (PEDOT) films using vacuum vapour phase polymerisation is reported. Water vapour is introduced into the chamber and results suggest that it acts as a proton scavenger during polymerisation. Process optimisation leads to PEDOT films that have high conductivity and a blue‐black appearance. Poor quality films have lower conductivity and a characteristic greenish colour. UV‐vis‐NIR spectra show that poor PEDOT films are characterised by higher absorption in the UV‐vis region and an absorption plateau in the NIR region, which suggests an increased level of disrupted conjugation along the polymer backbone or higher oligomer content. Conversely, high quality PEDOT is characterised by an extended NIR absorption tail and lower absorption in the UV‐vis region.
A template‐free method is described to fabricate continuous‐phase, porous polymer films by simultaneous phase separation during vapor deposition polymerization. The technique involves concurrent polymerization, crosslinking, and phase separation of condensed species and reaction products. Deposited films form open‐cell, macroporous structures consisting of crosslinked and glassy poly(glycidyl methacrylate). By limiting phase separation during vapor phase deposition, spatially dependent morphologies, such as layered morphologies, can be grown. Results show that combining vapor deposition polymerization with phase separation establishes morphological control, which may be applied to applications including cellular scaffolds, thin cushions and vibration dampers, and membranes for separations.
Furan ring‐functionalized solid surfaces are achieved by the initiated chemical vapor deposition (iCVD) method, a solvent‐free process to form films under mild conditions. The polymerization of furfuryl methacrylate monomer is initiated by a resistively heated filament wire. The functionality of the furan group in the iCVD film enabled Diels–Alder chemistry with 4‐phenyl‐1,2,3‐triazolin‐3,5‐dione (N‐PTD).
The oxidant, Fe(III) tosylate, was used in the vapour phase polymerisation (VPP) of PEDOT. The amphiphilic co‐polymer poly(ethylene glycol‐ran‐propylene glycol) was added and its influence examined. Both the PEDOT conductivity and optical contrast range increased with the inclusion of the co‐polymer, with the maximum being recorded at 4 wt.‐%. Loadings higher than this resulted in a systematic decrease in both conductivity and optical contrast. Evidence indicates that in addition to the beneficial anti‐crystallisation effect to the oxidant layer, the co‐polymer also reduces the effective reactivity of the oxidant, as demonstrated by slower polymerisation rates. Confirmation of the change in polymerisation rate was obtained using a quartz crystal microbalance (QCM). The slower polymerisation rate results in higher conductivity and optical contrast; however, XPS data confirmed that the co‐polymer remained within the PEDOT film post‐washing and this result explains why the performance decreases at high surfactant loadings.
The polymerization of methyl methacrylate (MMA) initiated by the system lysozyme, copper(II) chloride, and water was carried out. The effect of the amount of each component on the conversion of MMA was studied. The polymerization proceeded through a radical mechanism. Urea, known to be a denaturing agent for protein, was able to promote the polymerization. On addition of urea, it was found that the following three reactions took place: (1) promotion of the polymerization of MMA with lysozyme, Cu(II) ion, and water by the unfolding of the third structure of lysozyme, (2) polymerization initiated by urea and Cu(II) ion, (3) polymerization initiated by the S-S bonds of lysozyme and urea. 相似文献
The first vapor‐phase deposition of poly(vinyl cinnamate) (PVCin) is reported. Initiated chemical vapor deposition (iCVD) is used to synthesize PVCin thin films with an average thickness of 100 nm. Free radical polymerization and cyclization reactions compete during the deposition process, with approximately 45% of the repeat units undergoing cyclization. Exposure to UV light (λ = 254 nm) induces dimerization (cross‐linking) of the PVCin, which is quantified using spectroscopic techniques. Approximately 90% of the free cinnamate moieties are dimerized at a UV dose of 300 mJ cm−2. PVCin is also incorporated into a copolymer with N‐isopropylacrylamide, which exhibits a characteristic change in hydrophilicity with temperature. The copolymer is selectively cross‐linked through a mask, and reversible swelling of patterns with 30 μm resolution is demonstrated by submerging the film in water.
A novel thermally responsive copolymer p(NIPAAm‐co‐DEGDVE) is synthesized using the substrate independent method of iCVD and exhibits a sharp lower critical solution temperature (LCST) transition centered at ≈28.5 ± 0.3 °C determined via quartz crystal microbalance measurements with dissipation monitoring (QCM‐D). Swelling with water below the LCST produces a reversible change of ≈3× in film thickness. The layer is conformal on nanostructured surfaces including MWCNT forests and electrospun nanofiber mats. Modified planar substrates exhibit ≈30°change in static contact angle over the LCST, while through conformal coating on nanostructured substrates changes in static contact angle up to 135° are achieved. Additionally, coated surfaces exhibit temperature sensitive BSA adsorption measured by QCM‐D and is reversible as shown through fluorescence imaging of a coated electrospun nanofiber mat.
Films of electrically conducting polymer, poly(3-methylthiophene), are dissolved in monomer-free solutions at positive potentials to become thin, whereas they are polymerized in monomer-rich solutions at the same potentials as for the dissolution. A question arises whether they are dissolved or polymerized in solutions including a given concentration of the monomer when a positive potential is applied to the film. Conditions of the competition between the polymerization and the dissolution were searched at potentiostatic experiments for poly(3-methylthiophene) films at various concentrations of monomers and potentials. The dissolution prevailed over the polymerization as the concentration decreased and the potential was less positive. Chronoamperometric currents exhibited oscillation under the competition conditions. The oscillation was explained in terms of the Lotka–Volterra model for a simple oscillation reaction, in which competitive species were the conducting polymer and the monomer. 相似文献
We report the synthesis of a series of block copolymers consisting of a rod‐like semiconducting poly(2,5‐di(2′‐ethylhexyloxy)‐1,4‐phenylenevinylene) (DEH‐PPV) block and a flexible poly(lactic acid) (PLA) block that can be selectively degraded under mild conditions. Such selectively degradable block copolymers are designed as self‐assembling templates for bulk heterojunction donor–acceptor layers in organic solar cells. A lamellar microphase‐separated domain structure was identified for block copolymers with PLA volume fractions between 29 and 79% in bulk and thin films using SAXS, TEM, and AFM. Depending on the ratio of the two blocks we find either lamellae oriented parallel or perpendicular to the substrate in thin films.
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