New Heteroaromatic Polymers Consisting of Alkyl‐ and Amino‐1,3,5‐triazine Units. Their Basic Optical Properties and n‐Type Time‐of‐Flight Drift Mobility

Summary: Alternating copolymers between substituted 1,3,5‐triazine (substituent = alkyl or amine) and thiophene or bithiophene are synthesized. The copolymer of amino‐1,3,5‐triazine with thiophene is soluble in organic solvents, transparent in most parts of the visible region, and photoluminescent. The copolymer receives electrochemical n‐doping with an E_pc of −2.08 V vs Ag⁺/Ag and shows a time‐of‐flight electron drift mobility of 2.0 × 10⁻⁴ cm² · V⁻¹ · s⁻¹, which is larger than that of widely used Al(8‐quinolinolato)₃.

Structure of the poly(1,3,5‐triazine)s.     

Nanosized‐Silica‐Reinforced Holographic Polymer‐Dispersed Liquid Crystals

Summary: Nanosized silicas added to holographic polymer‐dispersed liquid crystals (HPDLC) provide the resin phase with increased elasticity, dimensional stability, and the high diffraction efficiency of the gratings. On the other hand, nucleation and growth of periodic modulation are delayed, especially with small‐sized silica because of the increased viscosity of the resin mixture. Effects of the LC/resin composition and cell gap on the diffraction efficiency have also been studied.

AFM image of silica added HPDLC.     

Synthesis of a Novel Fused Thiophene‐thieno[3,2‐b]thiophene‐thiophene Donor Monomer and Co‐polymer for Use in OPV and OFETs

The synthesis of a novel fused hexacyclic electron rich monomer incorporating thieno[3,2‐b]thiophene is reported and characterized by single crystal X‐ray diffraction. Suzuki co‐polymerization with benzothiadiazole (BT) afforded a novel low band‐gap polymer P4TBT with high molecular weights and good solution processability. Bulk heterojunction solar cell devices using the P4TBT and [70]PCBM gave power conversion efficiencies of 2.5%. Top‐gate, bottom‐contact field effect transistors (FETs) using P4TBT displayed high hole mobilities of 0.07 cm² · Vs⁻¹ demonstrating the suitability of the novel monomer and polymer for use in high performing organic electronic devices.

     

Unique Insertion Mode of 1,7‐Octadiene in Copolymerization with Ethylene by a Constrained‐Geometry Catalyst

Summary: The copolymerization of ethylene and 1,7‐octadiene (OD) was investigated with a constrained‐geometry catalyst. The ¹³C NMR spectrum of the copolymer indicated cyclization insertion of the OD unit in the penultimate position after a single ethylene insertion step. This unique insertion mode of OD forms a 1,5‐disubstituted cyclononane unit in the main chain of polyethylene.

Copolymerization of ethylene and 1,7‐octadiene (OD) with a constrained‐geometry catalyst.     

Low‐Rate Propylene Slurry Polymerization: Morphology and Kinetics

Summary: “True” initial polymerization rates can be calculated from the adiabatic temperature rise under isoperibolic conditions. They are much higher than initial polymerization rates measured by standard mass flow meter methods under quasi‐steady‐state conditions. These high initial rates are followed by a fast apparent deactivation (“attenuation”) until a constant (“plateau”) activity is reached at low polymerization yields of 2–3 g PP · (g catalyst)⁻¹ caused by an “increasing degree of encapsulation” of active sites. Mass transfer limitations are not observed. Cross sectional SEM images of the polymer samples support these kinetic findings.

Rate of polymerization (g of PP · (g catalyst)⁻¹ · h⁻¹) and yield of polymerization (g of PP · (g catalyst)⁻¹) as function of time.     

Fabrication of Metal‐Block‐Copolymer Composite Films by a Palladium‐Catalyzed Electroless Nickel‐Plating Process

Summary: Homogeneous films of PI‐b‐PDMAEMA are prepared on top of silicon (100) substrates. The free film surface shows microdomains of PDMAEMA within a PI matrix. These microdomains act as templates for the highly site‐selective synthesis of metal nanoparticles via palladium‐catalyzed electroless nickel plating. The particle formation is studied by atomic force microscopy in tapping mode and implications for a redox reaction and a nanoparticle growth mechanism on the surface of nanopatterned films are discussed.

Chemical structure of the PI‐b‐PDMAEMA copolymer and AFM phase image of a PI‐b‐PDMAEMA film on Si (100) substrate.     

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.

     

Azide/Alkyne‐“Click”‐Reactions of Encapsulated Reagents: Toward Self‐Healing Materials

The successful encapsulation of reactive components for the azide/alkyne‐“click”‐reaction is reported featuring for the first time the use of a liquid polymer as reactive component. A liquid, azido‐telechelic three‐arm star poly(isobutylene) ( = 3900 g · mol⁻¹) as well as trivalent alkynes were encapsulated into micron‐sized capsules and embedded into a polymer‐matrix (high‐molecular weight poly(isobutylene), = 250 000 g · mol⁻¹). Using (Cu^IBr(PPh₃)₃) as catalyst for the azide/alkyne‐“click”‐reaction, crosslinking of the two components at 40 °C is observed within 380 min and as fast as 10 min at 80 °C. Significant recovery of the tensile storage modulus was observed in a material containing 10 wt.‐% and accordingly 5 wt.‐% capsules including the reactive components within 5 d at room temperature, thus proving a new concept for materials with self‐healing properties.

     

Synthesis of a New Thiophene/Quinoxaline CT‐Type Copolymer with High Solubility and Its Basic Optical Properties

A new π‐conjugated charge‐transfer‐type copolymer of electron‐donating thiophene and electron‐accepting quinoxaline was prepared by organometallic polycondensation. The polymer was soluble in organic solvents such as tetrahydrofuran, and showed a UV‐vis peak at long wavelengths of 598 nm in chloroform and 629 nm in the film. Its film exhibited a χ⁽³⁾ peak in the resonance region with a χ⁽³⁾ value comparable to that of regioregular head‐to‐tail poly(3‐hexylthiophene‐2,5‐diyl).

     

Ambipolar Field‐Effect Transistor (FET) and Redox Characteristics of a π‐Conjugated Thiophene/1,3,4‐Thiadiazole CT‐Type Copolymer

Summary: A π‐conjugated charge transfer‐type copolymer consisting of an electron‐donating thiophene and an electron‐accepting 1,3,4‐thiadiazole, P(ThdzTh), underwent facile electrochemical p‐ and n‐doping, as revealed by cyclic voltammetry. The copolymer gave a new ambipolar field‐effect transistor (FET), which showed typical I_DS (source–drain current)–V_DS (source–drain voltage) curves in both a p‐type working mode and an n‐type working mode. In the n‐type working mode, the polymer showed a carrier mobility of about 5 × 10⁻³ cm² · V⁻¹ · s⁻¹ and an on/off ratio of about 3 × 10⁴.

n‐Channel field‐effect transistor characteristics of P(ThdzTh).     

Isobutene Polymerization Using [CuII(NCMe)6]2+ with Non‐Coordinating Anions as Catalysts

Cu^II compounds coordinated octahedrally with nitriles and associated with bulky, non‐coordinating counter ions can be applied in the polymerization of isobutene at 30 °C. High yields and a high content of terminal double bonds are reached in the resulting highly reactive polyisobutylenes, while the molecular masses are moderate. Two of the coordinating nitriles are more weakly coordinated than the other four, as can be concluded from an exemplary X‐ray structure and from vibrational spectra, thus providing easily accessible sites for substrate coordination.

     

Conjugated Microporous Networks on the Basis of 2,3,5,6‐Tetraarylated Diketopyrrolo[3,4‐c]pyrrole

π‐Conjugated microporous networks have been prepared from the tetraarylated diketopyrrolo[3,4‐c]pyrrole unit as a tetrafunctional building block. The reactions are carried out using microwave‐assisted Yamamoto or Sonogashira cross‐coupling. Red insoluble powders are obtained, showing intense fluorescence. The polymer networks exhibit a high gas storage capability, with BET surface areas up to about 500 m² · g⁻¹.

     

Dendritic Carrier Based on PEG: Design and Degradation of Acid‐sensitive Dendrimer‐like Poly(ethylene oxide)s

Degradable dendrimer‐like PEOs were designed using an original ABC‐type branching agent featuring a cleavable ketal group, following an iterative divergent approach based on the anionic ring opening polymerization (AROP) of ethylene oxide and arborization of PEO chain ends. A seventh generation dendrimer‐like PEO carrying 192 peripheral hydroxyls and exhibiting a molar mass of 446 kg · mol⁻¹ was obtained in this way. The chemical degradation of these dendritic scaffolds was next successfully accomplished under acidic conditions, forming linear PEO chains of low molar mass (≈2 kg · mol⁻¹), as monitored by ¹H NMR, SEC, and MALDI‐TOF mass spectrometry as well as by AFM.

     

Thioketone‐Mediated Polymerization of Butyl Acrylate: Controlling Free‐Radical Polymerization via a Dormant Radical Species

It is demonstrated by experiment and simulation that the commercially available thioketone 4,4‐bis(dimethylamino)thiobenzophenone is capable of controlling AIBN‐initiated bulk butyl acrylate polymerization at 80 °C. On the basis of molecular weight data and from monomer conversion versus time curves, the associated rate parameters are estimated. The addition rate coefficient, k_ad, for the reaction of a propagating chain with the thioketone is close to 10⁶ L · mol⁻¹ · s⁻¹ and the fragmentation rate coefficient, k_frag, is around 10⁻² s⁻¹ giving rise to large equilibrium constants in the order of 10⁸ L · mol⁻¹. Furthermore, cross‐ and self‐termination of the dormant radical species are identified to be operational.

     

Chemical Dual‐Responsive Wettability of Superhydrophobic PANI‐PAN Coaxial Nanofibers

PANI‐PAN coaxial nanofibers have been prepared by electro‐spinning during polymerization. The surface of the resulting nanofibers is superhydrophobic with a water contact angle up to 164.5°. Conductivity of the PANI‐PAN nanofibers is about 4.3 × 10⁻² S · cm⁻¹. The superhydrophobic nanofibers show a chemical dual‐responsive surface wettability, which can be easily triggered by changing pH value or redox properties of the solution. A reversible conversion between superhydrophobicity and superhydrophilicity can be performed in a short time. The strategy used here may provide an easy method to control the wettability of smart surfaces by using properties of low‐cost functional polymers.

     

Poly(3,4‐ethylenedioxythiophene) (PEDOT)‐Coated MWCNTs Tethered to Conducting Substrates: Facile Electrochemistry and Enhanced Coloring Efficiency

Composite films of poly(3,4‐ethylenedioxythiophene) (PEDOT)‐coated over functionalized multiwalled coiled and linear carbon nanotubes (CNTs) have been fabricated by a simple oxidative electropolymerization route. The nanotubular morphology of the polymer–CNT composite is responsible for the lower charge transfer impedance, lower internal resistance, and superior capacitive response in comparison to that shown by the control PEDOT film doped by trifluoromethanesulfonate ions. This facile electrochemistry exhibited by the PEDOT–CNT composite film ensues in a remarkably high coloration efficiency of 367 cm² · C⁻¹ at 550 nm, hitherto unrealized for PEDOT; thus demonstrating the huge potential the PEDOT–CNT composite film has as cathode for the entire spectrum of electrochromic devices.

     

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.

     

Smart Surface of Gold Nanoparticles Fabricated by Combination of RAFT and Click Chemistry

A simple efficient post‐modification route to the fabrication of hybrid gold nanoparticles with poly(N‐isopropylacrylamide) (PNIPAm) based on click chemistry is described. The PNIPAm was prepared by reversible addition fragmentation chain transfer radical polymerization (RAFT). The PNIPAm was immobilized onto gold nanoparticles with grafting densities of 5.8 chains · nm⁻² by a click reaction. The hybrid gold nanoparticles showed a temperature responsive phenomenon as the temperature changed between 20 and 45 °C.

     

Towards Multipotent Coatings: Chemical Vapor Deposition and Biofunctionalization of Carbonyl‐Substituted Copolymers

Future advances in designing bioactive materials, such as antithrombotic coatings for cardiovascular stents, will require widely applicable and robust methods of surface modification. In this paper, we report on the development of multifunctional polymer coatings made by chemical vapor deposition (CVD) copolymerization. Polymer coatings of various [2.2]paracyclophane derivatives were co‐deposited in controlled ratios and their chemical composition verified by FT‐IR and X‐ray photoelectron spectroscopy. Furthermore, preliminary biocompatibility of these coatings was assessed using human umbilical vein endothelial cells and 3T3 murine fibroblasts. The parallel immobilization of two different antithrombotic biomolecules onto a CVD‐based copolymer is also demonstrated by orthogonal immobilization strategies.