Photomechanical Switching Behavior of Semi‐Interpenetrating Polymer Network Consisting of Azobenzene‐Carrying Crosslinked Poly(vinyl ether) and Polycarbonate

Summary: A novel semi‐interpenetrating polymer network (semi‐IPN) with photomechanical switching ability was developed by a cationic copolymerization of azobenzene‐containing vinyl ethers in a matrix of a linear polycarbonate (PC). The semi‐IPN film showed reversible deformation upon switching the UV irradiation on and off and responded with unprecedented rapidity. The photomechanical effect is attributed to a reversible change between the highly aggregated and dissociated states of the azobenzene groups.

The reversible UV response of the length of the semi‐IPN film at 25 °C.     

A New Crystal Form,Polymorphism, and Multi‐Morphology in Biodegradable Poly(3‐hydroxypropionate)

Summary: A new crystal morphology (δ form) of poly(3‐hydroxypropionate) (PHP) is found in cast and melt‐crystallized PHPs with low molecular weight, in which the PHP chains possibly adopt a 2₁ helix rather than the trans conformation found in the β or γ form. The fusion temperature‐ and the crystallization temperature‐dependent polymorphism are responsible for the dual morphologies and the unique growth kinetics of spherulites in the melt‐crystallized PHPs.

a) A dual‐morphology developed at 70 °C in PHP films after melting at 117 °C and b) that formed during cooling at a rate of 1 °C · min⁻¹ from 130 °C.     

Preparation of Poly(1,3,4‐oxadiazole‐2,5‐diyl‐1,2‐vinylene) via Anionic Mechanism

2,5‐Bis(chloromethyl)‐1,3,4‐oxadiazole was synthesized and dehydrohalogenation of this model compound was investigated under various base conditions. The formation of an intermediate with quinodimethane‐type structure is suggested for reaction in EtONa/EtOH. Polymerization of this intermediate proceeds via an anionic mechanism to form poly(1,3,4‐oxadiazole‐2,5‐diyl‐1,2‐vinylene). Polymerization at a toluene/water interface results in shorter polymerization times, milder conditions, higher molecular weights, higher yields and fewer defects in the polymer as compared to the corresponding polycondensation route.

     

Fluorene‐Based Co‐polymer with High Hole Mobility and Device Performance in Bulk Heterojunction Organic Solar Cells

A new donor–acceptor polymer based on 9,9‐dioctylfluorene is synthesized and tested in organic photovoltaic devices. Results show that the polymer exhibits good solubility in a range of organic solvents and has a high hole mobility. When blended with a PC₇₀BM acceptor and fabricated into a bulk heterojunction, photovoltaic devices having a maximum power conversion efficiency (PCE) of 6.2% and a peak external quantum efficiency of 74% are created. Such efficiencies are realized without any necessity for solvent additives or thermal annealing protocols.

     

Highly Extensible Bio‐Nanocomposite Fibers

Here, we show that a poly(ethylene oxide) polymer can be physically cross‐linked with silicate nanoparticles (Laponite) to yield highly extensible, bio‐nanocomposite fibers that, upon pulling, stretch to extreme lengths and crystallize polymer chains. We find that both, nanometer structures and mechanical properties of the fibers respond to mechanical deformation by exhibiting strain‐induced crystallization and high elongation. We explore the structural characteristics using X‐ray scattering and the mechanical properties of the dried fibers made from hydrogels in order to determine feasibility for eventual biomedical use and to map out directions for further materials development.

     

Photo‐Induced Solid‐State Crosslinking of Electrospun Poly(vinyl alcohol) Fibers

Summary: Poly(vinyl alcohol) (PVA) was derivatized by polymer analogous reaction with thienyl acryloyl chloride and processed to submicrometer fibers by electrospinning from aqueous solution. Water solubility of otherwise water‐soluble PVA fibers was reduced considerably by UV crosslinking of thienyl acrylate modified PVA fibers in the solid state. Water stability of these crosslinked fibers was proven by water steam test at 95 °C.

UV/Vis spectrum of PVA‐Thio fibers irradiated for different periods at 300 nm.     

Rings of Hydrogel Fabricated by a Micro‐Transfer Technique

Microgel rings have been fabricated on a glass surface by a micro‐transfer technique. The polymer melt is transferred to the substrate surface in a confined space with a picoliter volume along the boundary of the polymeric stamp. The surface of the polymer features is smoothened by surface tension in an annealing cycle, which results in isotropic rings. After cross‐linking, the microgels respond swiftly when immersed in water. Asymmetric rings are also obtained by tilting the substrate. The microgels can detach from the substrate to form a suspension of the rings. Conjugated rings have also been fabricated by supplementing functional molecules into the poly(ethylene glycol) network.

     

A Soluble High Molecular Weight Copolymer of Benzo[1,2‐b:4,5‐b′]dithiophene and Benzoxadiazole for Efficient Organic Photovoltaics

The synthesis and characterization of a soluble high molecular weight copolymer based on 4,8‐bis(1‐pentylhexyloxy)benzo[1,2‐b:4,5‐b′]dithiophene and 2,1,3‐benzoxadiazole is presented. High efficiency organic photovoltaic (OPV) devices comprised of this polymer and phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) were fabricated by additive processing with 1‐chloronapthalene (CN). When the active layer is cast from pristine chlorobenzene (CB), power conversion efficiencies (PCEs) average 1.41%. Our best condition—using 2% chloronapthalene as a solvent additive in CB—results in an average PCE of 5.65%, with a champion efficiency of 6.05%.

     

A Model for Flow‐enhanced Nucleation Based on Fibrillar Dormant Precursors

A model for flow‐enhanced nucleation is presented based on the concept of a polymer melt containing a fixed number of nucleation precursors with a fixed size distribution. Depending on the size, precursors can either be active (i.e. susceptible to nucleation, the characteristic time scale of which is governed by the deformation rate) and grow into a spherulite or remain dormant. The size distribution of precursors is derived by combining nucleation theory and experimentally determined quiescent spherulite number densities. Longitudinal precursor growth, causing activation of dormant precursors, is a function of molecular deformation: the stretch of high molecular weight chains. Both the eXtended Pom‐Pom and the Rolie‐Poly model are tested to calculate the molecular deformation. A quantitative agreement is found between simulations and experimental results.

     

Isomérie Polyédrique dans des Spirophosphoranes Possédant le Groupement P?H

We have studied the temperature dependence of NMR spectra of six spirophosphoranes of the general formula: Experimental data show intramolecular isomerism which was explained by pseudo-rotation mechanism (Berry, Lit. 1). In all cases except one we also observed tautomerism between spirophosphorane and phosphite forms.     

Low‐Temperature Restructuring Processes in Polyhydrosilanes

Summary: This paper presents the structural influence of the Si H functionality on the physicochemical properties of polysilanes. New low‐temperature restructuring processes were discovered using thermal analysis (TGA, DSC). Photoluminescent (FL) and X‐ray photoelectron spectroscopy (XPS) measurements revealed the optoelectronic properties‐chemical structure relationship of the synthesized polymers.

Highly reactive Si H groups lead to restructuring of the main polysilane chain.     

Microstructure,Kinetics, and Transport in Oil‐in‐Water Microemulsion Polymerizations

The kinetics of microemulsion polymerization depend on the structure of the initial microemulsion and the transport of species between the aqueous domain, the micelles, and the polymer particles. The water solubility of the monomer and the proximity of the initial microemulsion composition to a phase boundary are key considerations for studying microemulsion polymerization kinetics and producing the desired products. Complications frequently arise in the synthesis of copolymers or the incorporation of controlled polymerization mechanisms because of the compartmentalized nature of microemulsion polymerizations.

     

Water‐Soluble Electrostatic Complexes of C60‐Anchored Anionic Polymers and Cationic Porphyrins

The preparation of novel highly water‐soluble electrostatic complexes from C₆₀‐anchored multi‐armed poly(acrylic acid)s and cationic porphyrin derivatives was demonstrated. The UV‐vis absorption and photoluminescence (PL) of these complexes show that the absorption of soret band exhibits a remarkable red shift and the emission of the Q band indicates an apparent quenching effect in comparison with that of the parent cationic porphyrin. These results imply a remarkable ground state and excited state interaction between the porphyrin ring and the C₆₀ moiety.

     

A Mixed Ruthenium Polypyridyl Complex Containing a PEG‐Bipyridine Macroligand

Summary: An amino‐functionalized bipyridine ligand was prepared in order to serve as a bridging unit to an activated low‐molecular‐weight monomethyl ether of poly(ethylene glycol) (PEG). Coordination of a ruthenium(II ) phenantroline precursor onto the formed PEG‐containing bipyridine ligand yielded a metal‐containing polymer which shows interesting properties for solar cell applications.

A schematic of the described polymeric ruthenium(II ) complex and its absorption and emission properties.     

A Lipase‐Responsive Vehicle Using Amphipathic Polymer Synthesized with the Lipase as Catalyst

We describe an enzyme‐responsive polymeric vehicle, which is of great interest in controlled drug delivery, biosensing, and other related areas. The polymer synthesized using lipase as catalyst in DMSO has a favorable molecular structure that is quickly hydrolyzed by lipase in aqueous phase, and allows a fast release of encapsulated molecules.

     

Precipitation Polymerization in Ethanol and Ethanol/Water to Prepare Uniform Microspheres of Poly(TMPTA‐styrene)

The precipitation polymerization of styrene‐trihydroxymethyl propane triacrylate has been carried out using ethanol and an ethanol/water mixture as the solvent. Uniform microspheres with high monomer conversion are achieved within 4 h, a much shorter polymerization time than that reported for the precipitation polymerization of divinyl benzene‐styrene in acetonitrile. The results clearly demonstrate that use of water as a co‐solvent is indeed very effective to promote the polymerization to high conversion and to obtain uniform microspheres. With no water under the otherwise same experimental conditions, only about 57% of monomer conversion is obtained; while the monomer conversion is remarkably increased to 96% when 12 vol.‐% of water is used.

     

A Composite Polymer Film with both Superhydrophobicity and Superoleophilicity

Summary: A composite film composed of porous polyurethane (PU) and polystyrene (PS) microspheres with both superhydrophobicity and superoleophilicity has been prepared. In this film, the dual‐scale structure enhances both the hydrophobicity and oleophilicity of the surface material. The composite film with such an ‘intelligent’ wettability property can be utilized to separate oil and water systems efficiently.

The composite film can be used to separate diesel oil and water.