A Novel Approach to Population Balance Modeling of Reactive Polymer Modification Leading to Branching

The mathematical treatment of polymer modification systems, described by population balances containing convolution is discussed. The two‐dimensional case (molecular weight vs. number of branch points) was considered by utilizing approximations of distributions, expanding them in terms of Gaussian basis functions. Three branching reactions were addressed: chain backbone to chain end point coupling; three‐functional coupling of chain ends; and crosslinking. The results were compared to those of Monte Carlo (MC) simulations. Good agreement was observed, although the quality of a distribution as generated by the numerical approach is much better in view of the strong scatter in the MC data.

     

An Improved Catalytic Method for Alkoxyamine Synthesis – Functionalized and Biradical Initiators for Nitroxide‐Mediated Radical Polymerization

Mn(salen)Cl was applied as a low‐cost catalyst for the formation of alkoxyamines from nitroxides and substituted styrenes. These “unimolecular initiators” for nitroxide‐mediated radical polymerization (NMRP) were synthesized using 2,2,6,6‐tetramethyl‐1‐piperidine‐1‐oxyl and 2,2,5‐trimethyl‐4‐phenyl‐3‐azahexane‐3‐oxyl. Functionalized alkoxyamines were obtained from 4‐vinylbenzyl chloride and 4‐vinylbenzyl alcohol. The divinyl compound 1,2‐bis(4‐vinylphenyl)ethane was converted to an alkoxyamine monomer and to bisaminooxy compounds, which can be used as “biradical initiators” for NMRP.

Formation of alkoxyamines using Mn(salen)Cl as the catalyst.     

Construction of a Hexameric Zn(II)‐metallomacrocycle and its Photo‐ and Electroluminescence Properties: [Zn6(O‐hexyl‐3,5‐bis(2,2′:6′,2″‐terpyridine)phenol)6(BF4)12]

Summary: An O‐hexyl‐3,5‐bis(terpyridine)phenol ligand has been synthesized and transformed into a hexagonal Zn(II)‐metallomacrocycle by a facile self‐assembly procedure capitalizing on terpyridine‐Zn(II)‐terpyridine connectivity. The structural composition was confirmed by NMR and mass spectral techniques; photo‐ and electroluminescence properties were also investigated. The OLED device shows green electroluminescent emission at 515 nm with a maximum luminance of 39 cd · m⁻² and maximum efficiency of 0.16 cd · A⁻¹.

Structure and electroluminescent properties of the metallomacrocycle investigated.     

Improved PEDOT Conductivity via Suppression of Crystallite Formation in Fe(III) Tosylate During Vapor Phase Polymerization

Vapor phase polymerization was used to synthesize high conductivity poly(3,4‐ethylenedioxyphenylene) (PEDOT). The monomer is presented to an oxidant‐rich substrate in vapor form and even for short polymerization times, 10–30 min, Fe(III) tosylate has a propensity for water absorption leading to crystal formation. Poor oxidant treatment before polymerization or high humidity during polymerization can create holes in the PEDOT film decreasing its conductivity. The addition of an amphiphilic copolymer poly(ethylene glycol)‐ran‐poly(propylene glycol) suppresses crystal growth allowing better film formation. The humidity level during synthesis was optimized at 35% relative humidity (RH), producing a conductivity of 761 S · cm⁻¹. Additionally, the copolymer extends the RH range that is tolerable for polymer synthesis.

     

Post‐Synthesis Functionalization of (Meth)acrylate Based Monoliths via Electron Beam Triggered Graft Polymerization

Porous polymeric monoliths were prepared via electron beam triggered free radical polymerization of (meth)acrylates. Post‐synthesis functionalization of these supports was accomplished via electron beam initiated free radical graft polymerization of methacryloyl‐substituted NHC precursors. The grafted precursors were converted into the corresponding copper complexes. Cu‐loadings were between 1.3 mg · g⁻¹ and 1.5 mg · g⁻¹. These supported catalysts were used in selected CO hydrosilylation and cyanosilylation reactions using a continuous flow setup.

     

Anisotropic Electronic Conductivity in Layer‐By‐Layer Composite Film Composed of Water‐Soluble Conjugated Polymers and SWNTs

This paper reports the anisotropic electrical properties of a layer‐by‐layer (LBL) film composed of water‐soluble conjugated polymers and single‐walled carbon nanotubes (SWNTs). The water‐soluble poly (p‐phenylene ethynylene)s (PPEs) are capable of a strong π‐π interaction with the sidewall of SWNTs and results in a very stable PPE‐SO₃/SWNTs composite in aqueous solution. Aligned LBL films were prepared by self‐assembly using the anionic PPE/SWNTs and cationic PPE on various substrates. The polarized Raman spectra exhibited the cos²α polarization dependence of the G‐band intensity between the polarization direction and the SWNTs alignment direction. The electric conductivity within the LBL films can be controlled by the deposition direction in the LBL formation.

     

All‐Conjugated,Rod‐Rod Block Copolymers‐Generation and Self‐Assembly Properties

Based on their rigid‐rod structure all‐conjugated, rod‐rod block copolymers show a preferred tendency to self‐assemble into low‐curvature vesicular or lamellar nanostructures independent from their specific chemical structure and composition. This unique and attractive behaviour is clearly illustrated in a few examples of such all‐conjugated block copolymers. The resulting nanostructured heteromaterials may find applications in electronic devices or artificial membranes.

     

Tuning the Properties of Functional Pyrrolidinium Polymers by (Co)polymerization of Diallyldimethylammonium Ionic Liquids

The synthesis and polymerization of novel diallyldimethylammonium ionic liquid monomers is described. A free‐radical polymerization follows a ring‐closing cyclopolymerization mechanism similar to the one observed previously for diallyldimethylammonium halides that leads to pyrrolidinium functional polymers. As previously observed in other families of polymeric ionic liquids, their physico‐chemical properties are seriously affected by the nature of the counter‐anion. As an example, the thermal stability increases following the trend SCN⁻ < < < bis(trifluoromethane)sulfonamide. Interestingly, this polymerization route may lead to the synthesis of a new family of random copolymers that have a similar poly(diallyldimethylammonium) backbone and a mixture of counter‐anions determined by the comonomer selection.

     

Spinning and Characterization of Conducting Microfibers

Conducting microfibers of poly(3,4‐ethylenedioxythiophene) doped with poly(4‐styrene sulfonate), having a diameter ranging between 4.6 and 16 μm, were fabricated by a wet‐spinning technique. The as‐spun microfiber had no notable orientation of polymer chains with poor crystallinity, and electrical conductivity was in the order of 10⁻¹ S · cm⁻¹ regardless of the diameter. Young's modulus, tensile strength, and elongation at break for the resulting microfiber were 1.1 ± 0.3 GPa, 17.2 ± 5.1 MPa, and 4.3 ± 2.3%, respectively.

SEM image of a PEDOT/PSS microfiber reported here.     

Fabrication of Aligned Polyaniline Nanofiber Array via a Facile Wet Chemical Process

In this work, we demonstrate for the first time a template free approach to synthesize aligned polyaniline nanofiber (PN) array on a passivated gold (Au) substrate via a facile wet chemical process. The Au surface was first modified using 4‐aminothiophenol (4‐ATP) to afford the surface functionality, followed subsequently by an oxidation polymerization of aniline (AN) monomer in an aqueous medium using ammonium persulfate as the oxidant and tartaric acid as the doping agent. The results show that a vertically aligned PANI nanofiber array with individual fiber diameters of ca. 100 nm, heights of ca. 600 nm and a packing density of ca. 40 pieces·µm⁻², was synthesized.

     

Novel Polymer Electrolyte Membrane,Based on Pyridine Containing Poly(ether sulfone), for Application in High‐Temperature Fuel Cells

Summary: Novel poly(aryl ether sulfone) copolymers containing 2,5‐biphenylpyridine and tetramethyl biphenyl moieties were synthesized by polycondensation of 4‐fluorophenyl sulfone with 2,5‐(4′,4″ dihydroxy biphenyl)pyridine and tetramethyl biphenyl diol. Copolymers with different molecular weights and different monomer compositions were obtained. These copolymers exhibit excellent film‐forming properties, mechanical integrity, and high modulus up to 250 °C, high glass transition temperatures (above 280 °C) as well as high thermal stability up to 400 °C. In addition to the above properties required for PEMFC application, this novel material shows high oxidative stability and acid doping ability, enabling proton conductivity in the range of 10⁻² S · cm⁻¹ above 130 °C.

Synthesis of copolymers with high acid uptake and ionic conductivity.     

Optical Non‐Linearity from Montmorillonite Intercalated with a Chromophore‐Containing Dendritic Structure: A Self‐Assembly Approach

Chromophore‐containing dendritic structures (G1, G2) are utilized to intercalate layered silicates, which results in a large d‐spacing up to 126 Å. An exfoliated morphology is obtained by mixing the dendritic structure intercalated layered silicates with polyimide in N,N‐dimethylacetamide solution. The dendritic structures attached on the clay template would arrange in a non‐centrosymmetric manner. This self‐assembled arrangement brought about the electro‐optical coefficients of 5–6 pm · V⁻¹ for these relatively low chromophore‐containing organic/inorganic nanocomposites without resorting to poling. Excellent temporal stability (100 °C) is also achieved.

     

Electrical Conductivity of an Individual Polyaniline Nanotube Synthesized by a Self‐Assembly Method

Camphor sulfonic acid (CSA) doped polyaniline (PANI) nanotubes (175 nm in outer diameter and 120 nm in inner diameter) were synthesized successfully by a self‐assembly method. It is found that the room‐temperature conductivity of an individual PANI nanotube is 30.5 S · cm⁻¹; in particular, the intrinsic resistance of an individual nanotube (30 kΩ) is much smaller than the contact resistance of crossed nanotubes (500 kΩ).

A SEM image of two crossed PANI‐CSA nanotubes and the attached Pt electrodes.     

New Approach to the Synthesis of Polyacrylamide in Miniemulsified Systems

Summary: A new approach to the preparation of water soluble polymer in inverse miniemulsions is proposed. A redox initiation system consisting of ceric ions and carbohydrate‐based surfactant Span 60 as a reducing agent is successfully used for the polymerization of AAm. This initiation system provides chain nucleation and growth near interfacial boundaries. As a result, stable uniform latex with particle radius of about 50–70 nm is obtained. The prepared PAAm has a rather high of up to about 2 × 10⁶ Da.

     

Controllable Optical,Electrical, and Morphologic Properties of 3,4‐Ethylenedioxythiophene Based Electrocopolymerization Films

This contribution presents a kind of novel and neutral network films based on EDOT formed by in situ electrocopolymerization (ECP). The ECP films which are neutral and colorless exhibit the conductivity of 0.2–0.5 S · cm⁻¹, W_F of 4.79–5.20 eV, and RMS roughness of 3.51–5.26 nm. The electroluminescent devices where ECP films acted as hole‐transport layer (HTL) exhibit higher brightness, current density, efficiency (20–30% improvement), and stability than that of PEDOT:PSS HTL device. The ECP films also significantly benefit the stability of neighboring organic layer compared to PEDOT:PSS. This kind of new ECP films affords more opportunities to develop organic light‐emitting diodes (OLEDs) with high performances and stability.

     

Low Water Swelling and High Proton Conducting Sulfonated Poly(arylene ether) with Pendant Sulfoalkyl Groups for Proton Exchange Membranes

Novel side‐chain‐type sulfonated poly(arylene ether) with pendant sulfoalkyl group copolymers (PSA‐SPAE‐6F) have been synthesized by direct copolymerization from a new sulfonated monomer, sodium 3‐(4‐(2,6‐difluorobenzoyl)phenyl)propane‐1‐sulfonate. The sulfonate content could be easily controlled by adjusting the sulfonated and the unsulfonated monomer feed ratio. The obtained copolymers all show good thermal and mechanical properties. It should be noted that the most highly sulfonated copolymer, PSA‐SPAE‐6F90 with an ion exchange capacity of 1.30 mequiv · g⁻¹, shows a proton conductivity of 0.11 S · cm⁻¹ and a water swelling ratio of only 12.9% at 100 °C, which indicates its high proton conductivity and excellent dimensional stability in hot water.

     

The Electrical Conductivity of Graphite Nanoplatelet Filled Conjugated Polyacrylonitrile

The electrical conductivity of composites of exfoliated graphite nanoplatelets (GNPs), including bromine‐doped GNP, and conjugated polyacrylonitrile has been investigated. The focal point is the dual nature of the graphite nanoparticles, which exhibit both intrinsic electrical conductivity and doping capability of semi‐conductive polymers such as conjugated polyacrylonitrile to form charge‐transfer complexes. The conductivity is particularly enhanced in conjugated polyacrylonitrile composites (e.g., with 6 wt.‐% graphite nanoplatelets) where the value rises from 1 × 10⁻¹⁰ to 2 × 10⁻³ S · cm⁻¹, which reflects jointly the conductivity of the doped semi‐conductive polymer together with the percolation‐based conductivity of the particles.

     

Polyelectrolyte Complexes Consisting of Macromolecules With Varied Stiffness: Computer Simulation

Monte Carlo simulations are employed in order to analyze the structure of polyelectrolyte complexes consisting of two identical but oppositely charged macroions with varying chain stiffness. It is shown that two complex structures can arise depending on the stiffness of the constituent chains. Stiff chains are organized into a “ladder” structure in which chains are located parallel to each other and monomeric units are arranged into ionic pairs according to their position in the chain. Flexible chains form a globular “scrambled‐egg” structure with a disordered position of monomer units. The conformational transition between the two structures proceeds as a phase transition.