Step‐Growth Radical Addition‐Coupling Polymerization (RACP) for Synthesis of Alternating Copolymers

We report a new type of step‐growth radical addition‐coupling polymerization (RACP) involving consecutive addition of carbon‐centered radical derived from α,α′‐dibromo dibasic ester to NO double bond of C‐nitroso compound followed by cross‐coupling of carbon‐centered radical and in situ formed nitroxyl radical, which produces alternating copolymers with high molecular weight and unimodal molecular weight distribution from saturated and unsaturated monomers.

     

Blue‐Light‐Emitting Conjugated Polymers Derived From 2,7‐Carbazoles

Blue‐light‐emitting 2,7‐carbazole‐based conjugated copolymers have been prepared by Yamamoto or Suzuki cross‐coupling reactions. By introducing highly substituted aromatic comonomers, fully soluble high‐molecular‐weight copolymers have been obtained. Moreover, these amorphous polymeric materials exhibit good thermal stability and interesting redox properties. All these features make these new conjugated polymers highly promising for the development of single‐polymer‐layer blue‐light‐emitting diodes.

     

Fluorinated Poly(aryl ether) Containing a 4‐Bromophenyl Pendant Group and its Phosphonated Derivative

Summary: A high‐molecular‐weight fluorinated poly(aryl ether) with a 4‐bromophenyl pendant group has been synthesized based on a bromo‐bisphenol. A phosphonic acid derivative is readily prepared from this in high conversion yield. The phosphonated polymer possesses excellent thermal, oxidative, and dimensional stability, low methanol permeability, and reasonable proton conductivity, and may be a candidate polymeric electrolyte membrane for fuel cell applications.

Synthesis of a poly(aryl ether) with a phosphonic acid group.     

Star Polyfluorenes with a Triphenylamine‐Based Core

Summary: Conjugated three‐ and four‐arm star polymers were successfully prepared by palladium catalyzed one‐pot Suzuki polycondensation of the multifunctional cores and an AB‐type monomer. The molecular weight of the star polymers could be controlled by the feed ratios of the monomers. The bromo end groups could be completely modified by fluorene mono boronic acid or triphenylamine mono boronic ester. The investigation of the optical, electrochemical, and thermal properties of the star polymers was also reported. All polymers exhibited good thermal stabilities and all the TPA‐capped polymers showed good hole‐transport abilities.

Preparation of three‐ and four‐arm star polyfluorences.     

Precision Sulfonic Acid Ester Copolymers

Linear ethylene copolymers containing sulfonic acid ethyl esters precisely spaced on every 21st carbon have been synthesized using metathesis polycondensation chemistry. These precision structures with one directly attached and one aromatic spaced sulfonic acid ester are synthesized with the goal of tailoring layered higher order morphologies in contrast to conventional clustered ionic polyolefins. Primary structural characterization confirms the precision polymer structures. Additional secondary microstructural analysis by DSC shows a recoverable endothermic melt transition of polyethylene‐like lamellae crystallites of the directly attached ester while completely amorphous behavior is observed when the ester is spaced away from the backbone with an aromatic group.

     

Polymer/Laponite Composite Latexes: Particle Morphology,Film Microstructure,and Properties

Transparent film materials with excellent mechanical and thermal properties were elaborated by drying a latex suspension of armored polymer/Laponite composite particles. Low‐temperature TEM observation of ultrathin cross‐sections of the films indicated a unique network morphology characterized by a “honeycomb” distribution of the Laponite platelets remindful of the original particles morphology.

     

Novel Spectrally Stable Saturated Blue‐Light‐Emitting Poly[(fluorene)‐co‐(dioctyldibenzothiophene‐S,S‐dioxide)]s

Novel poly[(fluorene)‐co‐(2,8‐dioctyldibenzothiophene‐S,S‐dioxide‐3,7‐diyl)]s were synthesized. The octyl group on the 2,8‐dioctyldibenzothiophene‐S,S‐dioxide (DOSO) unit improved the solubility of the polymers and broadened the optical band gap from 2.95 to 3.20 eV as the content of DOSO unit increases. The electroluminescence (EL) spectra of polymers show CIE coordinates around (0.16, 0.07) independent of the ratio of DOSO units in the polymers, owing to the ICT and steric hindrance dual‐function. A high efficiency of 3.1 cd · A⁻¹ (EQE = 3.9%) was obtained with the configuration of ITO/PEDOT:PSS/polymer/Ba/Al. The results indicate that PF‐3,7DOSOs could be a promising candidate for saturated blue‐emitting polymers with spectral stability and high efficiency.

     

Synthesis and Characterization of Novel Mesogen‐Jacketed Liquid Crystalline Miktoarm Star Rod‐Coil Block Copolymer

Summary: A series of novel mesogen‐jacketed liquid crystal miktoarm star rod‐coil block copolymers were synthesized via atom transfer radical polymerization (ATRP). Their architectures {coil conformation of styrene segment and rigid rod conformation of {2,5‐bis[(4‐methoxyphenyl)oxycarbonyl]styrene} (MPCS) segment} were confirmed by GPC, ¹H NMR, and MALDI‐TOF studies. The liquid crystalline behaviors of the synthesized copolymers are evidenced from POM observation. The liquid crystalline phase depends on the molecular weights of the rigid rod arm of miktoarm star copolymers.

Miktoarm star rod‐coil block copolymer.     

Enhanced Conductivity of Polyaniline by Conjugated Crosslinking

A novel crosslinked conductive polyaniline (PANI) was prepared by chemically copolymerizing aniline (An) and p‐phenylenediamine (PPDA) with triphenylamine (TPA) as crosslinker, using ammonium peroxydisulfate (APS) as an oxidant. The effects of different preparation conditions on the electrical conductivity of polymers were systematically investigated by adjusting acid kinds, concentration, the ratio of APS/An, the mounts of TPA and PPDA. The crosslinked PANI displayed a conductivity increase of up to 25% compared with the linear one. Their structures were characterized by Fourier‐transformed infrared spectroscopy and X‐ray photoelectron spectroscopy, and the electrical conductivity was also tested by a typical four‐point probe (RTS‐8) technique.

     

Novel Chromophore‐Functionalized Poly[2‐(trifluoromethyl) adamantyl acrylate‐methyl vinyl urethane]s with High Poling Stabilities of the Nonlinear Optical Effect

Nonlinear optical vinyl polymers with high glass transition temperature (T_g) were prepared by the functionalization of a fluorinated acrylate‐methyl vinyl isocyanate copolymer. A modified pathway to obtain a thiophene bridged chromophore was worked out. Poled films of the polymers show a fairly high and stable nonlinear optical response, even at elevated temperatures.

The thiophene‐bridged chromophore, based on a substituted dicyanomethylene‐dihydrofuran acceptor, synthesized here.     

Novel Cross‐Linked Films Prepared from Hyperbranched Poly(amine‐ester)

Summary: Novel hyperbranched poly(amine‐ester) (HPAE) cross‐linked films were prepared by cross‐linking the terminal hydroxyl groups of HPAE using glutaraldehyde (GA). Atom force microscope and scanning electron microscope revealed their smooth surfaces, dense and homogenous matrices. Property characterizations indicated that these cross‐linked films had good hydrophilicity, relative low protein adsorption, and high tensile strength. Also, their swelling behavior varied with the solvent.

Structure of the hyperbranched poly(amine‐ester).     

Stereoselective Cyclopolymerization of Polar 1,6‐Heptadiynes by Novel,Tailor‐Made Ruthenium‐Based Metathesis Catalysts

Summary: The cyclopolymerization of 4,4‐bis(hydroxymethyl)‐1,6‐heptadiyne ( M1 ), 4‐(carboxyethyl)‐1,6‐heptadiyne ( M2 ), 4‐(hydroxymethyl)‐1,6‐heptadiyne ( M3 ), and 4‐carboxy‐1,6‐heptadiyne ( M4 ) using five different well‐defined metathesis initiators was investigated. Control of molar mass was achieved with catalysts bearing trifluoroacetate ligands. ¹³C NMR experiments showed that poly‐ M2 , prepared by the action of any catalyst consisted solely of five‐membered ring structures, i.e., 1,2‐(cyclopent‐1‐enylene)vinylene units. Effective conjugation lengths of all polymers were calculated from the corresponding UV‐Vis absorption maxima, which varied reversibly with temperature.

     

Polymer Brushes via Controlled,Surface‐Initiated Atom Transfer Radical Polymerization (ATRP) from Graphene Oxide

A method for growing polymers directly from the surface of graphene oxide is demonstrated. The technique involves the covalent attachment of an initiator followed by the polymerization of styrene, methyl methacrylate, or butyl acrylate using atom transfer radical polymerization (ATRP). The resulting materials were characterized using a range of techniques and were found to significantly improve the solubility properties of graphene oxide. The surface‐grown polymers were saponified from the surface and also characterized. Based on these results, the ATRP reactions were determined to proceed in a controlled manner and were found to leave the structure of the graphene oxide largely intact.

     

Synthesis and Characterization of a Novel Calix[4]arene‐Based Periodic Mesoporous Organosilica

Summary: A new calix[4]arene‐based periodic mesoporous organosilica has been synthesized using tetraethoxysilane (TEOS) and a calix[4]arene‐based silane monomer as the precursors and cetyltrimethylammonium bromide (CTAB) surfactant as the structure‐directing template, and is shown to be capable of visual detection and entrapment of NO₂.

Synthesis of the novel mesoporous organosilica material containing covalently bound tetra‐O‐alkylated calix[4]arene hosts.     

Synthesis of Multiblock Polymer Containing Narrow Polydispersity Blocks

Summary: We have developed a new strategy to prepare multiblock polymers and copolymers via one‐ or two‐step polymerization using a polymerizable cyclic trithiocarbonate (CTTC), 4,7‐diphenyl‐[1,3]dithiepane‐2‐thione. CTTC undergoes ring‐opening process to incorporate a trithiocarbonate moiety. The trithiocarbonate moiety in turn, functions as a reversible addition fragmentation chain transfer (RAFT) agent. Through this mechanism, multiblock polystyrenes and polystyrene‐block‐ poly(butyl acrylate) copolymers containing various narrow polydispersity blocks can be prepared.

Integrated process of ring‐opening and RAFT polymerizations involving cyclic trithiocarbonates.     

Micelles Formed by Cylindrical Brush‐Coil Block Copolymers

Summary: Amphiphilic cylindrical brush‐coil block copolymers consisting of a polystyrene coil and a cylindrical brush block with poly(acrylic acid) side chains are prepared by ATRP of t‐butylacrylate from a block comacroinitiator. Upon acidolysis of the poly(t‐butylacrylate), water‐soluble polymers were obtained that were observed to form micelles consisting of 4–5 block copolymers on average in aqueous solution. The star‐like nature of such micelles was clearly visualized by scanning force microscopy.

Schematic of coil‐cylindrical brush block copolymer PS‐b‐(PⁱBEMA‐g‐PAA), its AFM image clearly showing the main chain and the PAA corona of the cylindrical brush block.     

Synthesis and Optical Properties of Dendronized Porphyrin Polymers

Summary: A novel kind of dendronized porphyrin polymers was synthesized by Sonogashira coupling of diethynyl‐functionalized porphyrin monomers and diiodo‐functionalized macromonomers bearing Fréchet‐type dendrons. The encapsulation of red‐light‐emitting porphyrin‐containing conjugated backbones into dendronized polymers can not only reduce the aggregation of polymer backbones and the self‐quenching of their fluorescence but also endow the porphyrin polymers with good solubility. We also report the optical and electrochemical properties of the porphyrin‐containing dendronized polymers.

Synthesis of a novel kind of dendronized porphyrin polymers by Sonogashira coupling of diethynyl‐functionalized porphyrin monomers and diiodo‐functionalized dendritic macromonomers.     

A Novel Route for Fabricating Metal‐Polymer Composite Nanoparticles with Phase‐Separated Structures

Au nanoparticles (NPs) and polymer composite particles with phase‐separation structures were prepared based on phase separation structures. Au NPs were successfully synthesized in amphiphilic block‐copolymer micelles, and then composite particles were formed by a simple solvent evaporation process from Au NPs and polymer solution. The phase separated structures (Janus and Core‐shell) were controlled by changing the combination of polymers having differing hydrophobicity.

     

Novel Acid‐Labile,Thermoresponsive Poly(methacrylamide)s with Pendent Ortho Ester Moieties

Novel acid‐labile, thermoresponsive methacrylamide‐based (co)polymers with pendent ortho ester groups were prepared by free radical polymerization of N‐(2‐methoxy‐1,3‐dioxan‐5‐yl) methacrylamide (NMM) and N‐(2‐ethoxy‐1,3‐dioxan‐5‐yl)methacrylamide (NEM). These polymers are both thermoresponsive and acid‐sensitive in aqueous solution, which was proved by transmittance measurements, fluorescence, and ¹H NMR spectroscopy. The LCSTs of the (co)polymers were shifted to higher temperature by increasing the content of the more hydrophilic NMM units. All of these polymers can be hydrolyzed under acidic condition and the hydrolysis rate increased with the decrease in the pH value.