Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 52 Issue 18

Early View (Online Version of Record published before inclusion in an issue)

Impact Factor: 3.543

ISI Journal Citation Reports © Ranking: 2012: 12/83 (Polymer Science)

Online ISSN: 1099-0518

Associated Title(s): Journal of Polymer Science Part B: Polymer Physics

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  1. 1 - 65
  1. Articles

    1. Tuning the LCST of poly(2-cyclopropyl-2-oxazoline) via gradient copolymerization with 2-ethyl-2-oxazoline

      Mathias Glassner, Kathleen Lava, Victor R. de la Rosa and Richard Hoogenboom

      Article first published online: 22 AUG 2014 | DOI: 10.1002/pola.27364

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      A series of P(c-PropOx-grad-EtOx) gradient copolymers were prepared by living cationic ring opening polymerization of 2-cyclopropyl-2-oxazoline and 2-ethyl-2-oxazoline. All copolymers showed a reversible LCST transition in aqueous solution. The cloud point temperature (TCP) decreased linearly with increasing mol fraction of c-PropOx, allowing accurate tuning of TCP over a wide temperature range. Surprisingly, the glass transition temperature of all copolymers were lower than those of the homopolymers indicating poor interchain miscibility.

    2. Synthesis and characterization of a biodegradable ABC triblock terpolymer as co-delivery carrier of doxorubicin and DNA

      Jiao Bian, Ying Hao, Jinlin He, Wenling Zhang, Mingzu Zhang and Peihong Ni

      Article first published online: 22 AUG 2014 | DOI: 10.1002/pola.27361

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      A new kind of cationic ABC triblock terpolymer PEEP-b-PCL-b-PDMAEMA has been successfully prepared via a combination of two-step ring-opening polymerization and atom-transfer radical polymerization reactions. The chemical structures, self-assembly behavior, in vitro enzymatic degradation, cytotoxicity, and pH-dependent controlled release of encapsulated DOX were investigated in detail. In addition, the study by a live cell imaging system further demonstrated that the polymer/DOX/DNA polyplexes could efficiently co-deliver DOX and GFP–DNA into HeLa cells, indicating that they may find potential applications for combinatorial cancer therapy.

    3. Modified soybean oil as a reactive diluent: Synthesis and characterization

      Priyanka P. Nalawade, Brinda Mehta, Coleen Pugh and Mark D. Soucek

      Article first published online: 22 AUG 2014 | DOI: 10.1002/pola.27352

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      Soybean oil was modified in two steps: (1) conjugation of soybean oil, (2) Diels-Alder addition with 3-(trimethoxysilyl)propyl methacrylate, 2,2,2-trifluoroethyl methacrylate and triallyl ether acrylate. 13C-1H gHSQC NMR spectra helped confirm the formation of a cyclohexene ring in all reactions, indicating a Diels-Alder addition. The diluent efficiency of modified soybean oil was evaluated in long oil alkyd formulation. Triallyl ether functionalized soybean oil resulted in the highest reduction in the viscosity of the alkyd formulations.

    4. Smart photoluminescent nanohybrids based on CdSe quantum dots capped with multidentate thiolated pH-responsive and thermoresponsive polymers for nanosensing

      Marta Liras, Elena Peinado, Pedro Cañamero, Isabel Quijada-Garrido and Olga García

      Article first published online: 22 AUG 2014 | DOI: 10.1002/pola.27358

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      Well-defined thermoresponsive polymers obtained by the atom transfer radical polymerization (ATRP) of MEOnMA (n = 2, 3, or 8) with small ratios of a thiolated comonomer (AcSEMA) can replace the hydrophobic trioctylphosphine oxide capping of CdSe quantum dots (QDs). After ligand exchange, the mild hydrolysis of the acetylthiol group into thiol is the key to enhance the QD luminescence. These copolymers endowed the final materials with their thermoresponsive and amphiphilic properties. The hybrids showed good water dispersability, lower critical solubility temperature around body temperature and, the most important, an abrupt increase of the fluorescence emission when the polymer collapses at acid media.

    5. Photo-induced thiol-ene polysulfide-crosslinked materials with tunable thermal and mechanical properties

      So Young An, Dong Geun Lee, Ji Won Hwang, Kyung Nam Kim, Joon Hyun Nam, Hyun Wook Jung, Seung Man Noh and Jung Kwon Oh

      Article first published online: 22 AUG 2014 | DOI: 10.1002/pola.27353

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      A versatile and effective approach is reported utilizing high-molecular-weight methacrylate copolymers, with pendant thiol and vinyl groups (MCPsh and MCPenes), to modulate the thermal and mechanical properties of photo-induced thiol-ene crosslinked materials.

    6. Block copolymers in the synthesis of gold nanoparticles. Two new approaches: Copolymer aggregates as reductants and stabilizers and simultaneous formation of copolymer aggregates and gold nanoparticles

      Angel Leiva, Irma Fuentes, Esteban Bossel, Marcela Urzúa, Maximiliano Méndez, Maximiliano Pino, Deodato Radić, Valeria Márquez and Fernando. D. González-Nilo

      Article first published online: 22 AUG 2014 | DOI: 10.1002/pola.27354

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      Two interesting methods for the synthesis of gold nanoparticles are reported. In the first, copolymer aggregates react with AuCl4, and nanoparticles surrounded by aggregates are obtained. In the second, nanoparticle formation takes place simultaneously with the aggregation of copolymers, resulting in copolymer aggregates with embedded gold nanoparticles.

  2. Rapid Communication

    1. Advanced photoresist technologies by intricate molecular brush architectures: Diblock brush terpolymer-based positive-tone photoresist materials

      Guorong Sun, Sangho Cho, Fan Yang, Xun He, Adriana Pavía-Sanders, Corrie Clark, Jeffery E. Raymond, Stanislav V. Verkhoturov, Emile A. Schweikert, James W. Thackeray, Peter Trefonas and Karen L. Wooley

      Article first published online: 22 AUG 2014 | DOI: 10.1002/pola.27362

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      The reported diblock brush terpolymer displays the fundamental advantages of high macromolecular and regiochemical control in simultaneous top-down/bottom-up construction of advanced positive-tone photoresist materials. By selective partition the substrate adhesion, surface-active migration, and chemically-reactive deblocking functional compositions into the cylindrical polymer brush architectures, large-areas of vertical alignment of the polymers within thin films are realized. The bottom-up premeditated system enables effective top-down lithography to produce near-molecular pixel resolution (2–3 molecules) at low operation dosage.

  3. Articles

    1. Temperature effect on template polymerization of methacrylic acid using stereocomplex formation on quartz crystal microbalance substrates

      Hiroharu Ajiro, Tatsuaki Ueyama and Mitsuru Akashi

      Article first published online: 21 AUG 2014 | DOI: 10.1002/pola.27350

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      Radical polymerizations of methacrylic acid in the porous isotactic-poly(methyl methacrylate) film, prepared by alternative layer-by-layer technique, were achieved at various temperatures. The results suggested that the thermal mobility of polymer chains is necessary to form stereocomplexes during the polymerization process, as evidenced by FT-IR spectral analyses.

    2. Preparation and self-assembly of stimuli-responsive azobenzene-containing diblock copolymers through microwave-assisted RAFT polymerization

      Po-Chih Yang, Hsin-Cheng Chen, Hua-Wen Wen and Po-I Wu

      Article first published online: 21 AUG 2014 | DOI: 10.1002/pola.27360

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      Two azobenzene-containing diblock copolymers were synthesized to investigate the effect of azobenzene on the photoisomerization kinetics and self-assembly behaviors of copolymers, by using sequential reverse addition-fragmentation transfer (RAFT) polymerization. Diblock copolymer, poly(StO54-b-Cazo9), showed lower photoisomerization rate constants (kt = 0.039 s−1) compared with Cazo monomer (kt = 0.097 s−1). Poly(StO54-b-Cazo9) takes advantage of the moderate self-assembly behavior of diblock copolymer to yield spherical micelles with a mean diameter of ∼238.3 nm in THF/H2O media.

    3. Chiral sensing of Eu(III)-containing achiral polymer complex from chiral amino acids coordination induction

      Chunhui Dai, Yuxiang Wang, Yiwu Quan, Qingmin Chen, Yixiang Cheng and Chengjian Zhu

      Article first published online: 18 AUG 2014 | DOI: 10.1002/pola.27356

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      A novel β-diketonate-based Eu(III)-containing polymer complex was designed as a CD probe for direct enantioselective recognition of N-Boc-proline enantiomers. The linear regression analysis of in situ CD sensing shows a good agreement between the magnitude of molar ellipticity and concentration of chiral N-Boc-l or d-proline, indicating that this kind Eu(III)-containing achiral polymer complex can be used as a chiral-sensing probe for enantioselective recognition of N-Boc-l or d-proline enantiomers based on Cotton effect of CD spectra.

    4. Revisiting thiol-yne chemistry: Selective and efficient monoaddition for block and graft copolymer formation

      Johannes K. Sprafke, Jason M. Spruell, Kaila M. Mattson, Damien Montarnal, Alaina J. McGrath, Robert Pötzsch, Daigo Miyajima, Jerry Hu, Allegra A. Latimer, Brigitte I. Voit, Takuzo Aida and Craig J. Hawker

      Article first published online: 18 AUG 2014 | DOI: 10.1002/pola.27345

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      Polymer coupling reactions are some of the most challenging chemical transformations due to low end-group concentration, steric hindrance, and decreased reactivity. Thiol-yne chemistry is shown to be a near-quantitative and selective strategy for the coupling of pre-formed polymers to give block and graft copolymers. With aromatic alkynes under a wide range of conditions, specific mono-addition is achieved with efficiencies surpassing those of traditional thiol-ene chemistry.

    5. The pH induced vesicle to micelle morphology transition of a THP-protected polymer

      Kay E. B. Doncom, Helen Willcock and Rachel K. O'Reilly

      Article first published online: 16 AUG 2014 | DOI: 10.1002/pola.27348

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      A diblock copolymer containing a protected acid block, a permanently hydrophobic block, and a charged hydrophilic end group was synthesized by RAFT polymerization. The polymer self-assembled into vesicles in aqueous solution, directed by the hydrophilic end group, and the removal of the protecting groups yielded an amphiphilic diblock copolymer, which exists as micelles in aqueous solution. The vesicle to micelle morphology was demonstrated by DLS and TEM.

    6. Evaluation of proton conductivity of sulfonated polyimide/dihydroxy naphthalene charge-transfer complex hybrid membranes

      Liana Christiani, Sandra Hilaire, Kazunari Sasaki and Masamichi Nishihara

      Article first published online: 14 AUG 2014 | DOI: 10.1002/pola.27343

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      Polymer coupling reactions are some of the most challenging chemical transformations due to low end-group concentration, steric hindrance, and decreased reactivity. Thiol-yne chemistry is shown to be a near-quantitative and selective strategy for the coupling of preformed polymers to give block and graft copolymers. With aromatic alkynes under a wide range of conditions, specific monoaddition is achieved with efficiencies surpassing those of traditional thiol-ene chemistry.

    7. Influence of linkage chemistry on folding, self-assembly, and photoresponse of amphiphilic azobenzene main chain polymers

      Zhilin Yu and Stefan Hecht

      Article first published online: 14 AUG 2014 | DOI: 10.1002/pola.27344

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      Two types of amphiphilic polymers, composed of azobenzene repeat units in the main chain connected either via ethynylene or butadiynylene linkages and carrying (chiral) oligo(ethylene glycol) side chains, have been synthesized via Sonogashira–Hagihara or Glaser polycondensation. Solvent titration experiments reveal that both polymers fold into stable helices in a polar environment. While the ethynylene-bridged polymer (PAzoE) resembles the behavior of its oligomeric counterparts, introduction of the extended diacetylene unit strengthens π,π-stacking interactions in case of the butadiynylene-bridged polymer (PAzoB), leading to a pronounced aggregation tendency and suppressing photoisomerization in the folded state.

    8. Synthesis of chiral iridium complexes immobilized on amphiphilic polymers and their application to asymmetric catalysis

      Shinichi Itsuno, Yosuke Hashimoto and Naoki Haraguchi

      Article first published online: 14 AUG 2014 | DOI: 10.1002/pola.27351

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      Polymerization of the achiral amphiphilic monomer, divinylbenzene, and polymerizable chiral 1,2-diamine monosulfonamide ligand results in a polymer-immobilized chiral ligand. Complexation of the polymeric chiral ligand with [IrCl2Cp*]2 affords the polymeric chiral complex, which has been successfully applied to asymmetric transfer hydrogenation of cyclic imines in both organic solvents and water to give chiral cyclic amines with a high level of enantioselectivity. The polymeric catalyst can be recycled many times without loss of the catalytic activity.

    9. Well-controlled ring-opening polymerization of cyclic esters catalyzed by aluminum amido complexes: Kinetics and mechanism

      Junpeng Liu and Haiyan Ma

      Article first published online: 13 AUG 2014 | DOI: 10.1002/pola.27359

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      A series of aluminum dimethyl complexes bearing bidentate amido ligands were synthesized and characterized. These complexes can initiate the ring-opening polymerizations of ε−CL and rac-LA in a well-controlled manner as single component catalysts and afford narrowly distributed PCLs or PLAs end-capped with the bidentate amido ligands, proving that the polymerizations of ε−CL and rac-LA are initiated via the insertion of monomer into the Al[BOND]N (amido) bond of the complexes.

    10. Importance of unpaired electrons in organic electronics

      Jonathan D. Yuen, Mingfeng Wang, Jian Fan, Dennis Sheberla, Moureen Kemei, Natalie Banerji, Mariateresa Scarongella, Sebastian Valouch, Toan Pho, Rajeev Kumar, Eneida C. Chesnut, Michael Bendikov and Fred Wudl

      Article first published online: 11 AUG 2014 | DOI: 10.1002/pola.27321

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      PBBTPD, a low bandgap, ambipolar conjugated donor-acceptor polymer based on benzobisthiadiazole (BBT), is shown to possess an open-shell singlet ground state as well as a thermally accessible triplet state. Theoretical predictions have suggested that such behavior is due to the biradicaloid character of BBT. This biradicaloid structure is in each BBT moiety and therefore PBBTPD is in fact a polyradicaloid. These observations will aid in development of better n-type polymeric acceptors for organic semiconductor applications.

  4. Rapid Communication

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      Poly(divinylbenzene-alt-maleic anhydride) nanoparticles as a novel stabilizer for Pickering polymerization of styrene

      Jian He, Dong Chen, Kai Han, Xiaoxia Huang, Liwei Wang, Jianyuan Deng and Wantai Yang

      Article first published online: 11 AUG 2014 | DOI: 10.1002/pola.27339

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      Poly(divinylbenzene-alt-maleic anhydride) nanoparticles with a narrow distribution and a diameter of 30 nm act as novel stabilizers in the Pickering emulsion polymerization of styrene. The hydrolyzed PDMNPs with NaHCO3 aqueous solution exhibited a very effective emulsification performance and a remarkably high emulsification efficiency. Raspberry-like PDMNPs/PS composite polymer particles have been successfully fabricated via copolymerization of pendant vinyl groups of PDMNPs with styrene.

  5. Foreword

  6. Articles

    1. “Kick-Starting” oxetane photopolymerizations

      James V. Crivello

      Article first published online: 8 AUG 2014 | DOI: 10.1002/pola.27329

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      The photoinitiated cationic ring-opening polymerizations of oxetane monomers exhibit long induction periods that make them unsuitable for many high-speed applications; 2,2-dialkyl-, 2,2,3-trialkyl- and 2,2,3,3,-tetraalkyl epoxides, as for example limonene dioxide and other terpene oxides, markedly accelerate oxetane photopolymerizations even at low concentrations. To account for these effects, a mechanism involving a modification of the initiation step of the ring-opening oxetane polymerization by the epoxide was proposed.

    2. An efficient nonisocyanate route to polyurethanes via thiol-ene self-addition

      Mariola Calle, Gerard Lligadas, Juan C. Ronda, Marina Galià and Virginia Cádiz

      Article first published online: 7 AUG 2014 | DOI: 10.1002/pola.27347

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      The synthesis of a nonisocyanate polyurethane was carried out via thiol–ene self-photopolymerization by using a carbamate monomer (AMC) including a thiol and double-bond end-functionalities. The thiol–ene carbamate monomer was synthesized from cysteamine and allyl chloroformate and therefore urethane group is directly into the precursor monomer. The high reactive AMC is successfully stabilized with pyrogallol (1% wt) as radical inhibitor. The obtained polyurethane presents semi-crystalline nature and very high thermal stability (T5% = ∼325 °C).

    3. Synthesis of amphiphilic homopolymers with high chain end functionality by SET–LRP

      Shampa R. Samanta, Ruilong Cai and Virgil Percec

      Article first published online: 7 AUG 2014 | DOI: 10.1002/pola.27331

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      For the first time SET–LRP of two amphiphilic acrylates, 2-methoxyethyl acrylate up to [M]0/[I]0 = 1000 and di(ethylene glycol) 2-ethylhexyl ether acrylate up to [M]0/[I]0 = 200 with very good control of molecular weight and molecular weight distribution is demonstrated in a common organic solvent, trifluoroethanol at 25 °C. Analysis of the chain end functionality of the resulting polymers demonstrates the synthesis of near-perfect chain-end functional homopolymers. This facile method opens up attractive possibilities for the fast synthesis of polymers with complex architecture under mild reaction conditions from amphiphilic monomers.

  7. Rapid Communication

    1. Free radical initiation mechanism based on the combination of alcohol initiators and borane activators

      Masahiro Ohkura and T. C. Mike Chung

      Article first published online: 7 AUG 2014 | DOI: 10.1002/pola.27337

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      A free radical initiation(R′[BOND]O[BOND]BR2) system is based on a combination of an alcohol (R′[BOND]OH) initiator and a dialkylborane (H[BOND]BR2) activator. Due to an empty p-orbital in the B atom, the C[BOND]O bond can be cleaved to form a reactive C• radical for initiating radical polymerization, while the stable •O[BOND]BR2 radical remains inactive. Considering the large availability of various alcohol moieties, this asymmetric initiation chemistry can be applied to supermolecular structures and surface modifications.

  8. Articles

    1. Synthesis and characterization of multiblock sulfonated poly(arylene ether sulfone) membranes with different hydrophilic moieties for application in polymer electrolyte membrane fuel cell

      Jinju Ahn, Hyejin Lee, Tae-Hyun Yang, Chang-Soo Kim and Byungchan Bae

      Article first published online: 6 AUG 2014 | DOI: 10.1002/pola.27330

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      Multiblock sulfonated poly(arylene ether sulfone)s were synthesized to investigate the structural effects on their membrane properties. Three different types of sulfonated hydrophilic blocks were used; their structures possessed different acidity and local concentration of sulfonic acid groups. The higher acidity and concentration of sulfonic acid groups resulted in higher proton conductivity under certain relative humidity conditions and phase.

  9. Highlights

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      Well-defined copolymers based on poly(vinylidene fluoride): From preparation and phase separation to application

      Vincent S.D. Voet, Gerrit ten Brinke and Katja Loos

      Article first published online: 6 AUG 2014 | DOI: 10.1002/pola.27340

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      Poly(vinylidene fluoride) (PVDF), exhibiting extraordinary physical, mechanical, and ferroelectric properties, is nowadays the second largest fluoropolymer in demand. Copolymerization of vinylidene fluoride with other fluoromonomers already resulted in a wide variety of commercial products. Well-defined block copolymers based on PVDF are potential precursors for functional nanostructured materials, and can find application in thermoplastic elastomers, membranes, surfactants and microelectronic devices. This Highlight provides an overview of the synthesis routes towards these materials and discusses their phase behavior and (potential) applications.

  10. Articles

    1. Conjugated polymer with rigid donor poly(para-divinylphenylamino) backbone and pendant cyanoacetic acid acceptor for dye sensitized solar cells

      Zhen Fang, Danlu Wu, Shahar Keinan and Bin Liu

      Article first published online: 6 AUG 2014 | DOI: 10.1002/pola.27334

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      A conjugated polymer with donor backbone and acceptor side group has been synthesized and utilized for dye-sensitized solar cells. The introduction of vinylene link in the polymer backbone leads to a broad absorption spectrum. DFT modeling suggests an efficient charge separation upon irradiation, which favors the electron injection to TiO2 conduction band. The DSSC cell exhibits a high peak IPCE and J-V response, with an overall power conversion efficiency of 3.67%.

    2. Nanosegregated polymeric domains on the surface of Fe3O4@SiO2 particles

      David Serrano-Ruiz, Paulino Alonso-Cristobal, Diego Mendez-Gonzalez, Marco Laurenti, Raúl Olivero-David, Enrique López-Cabarcos and Jorge Rubio-Retama

      Article first published online: 6 AUG 2014 | DOI: 10.1002/pola.27338

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      Mixed polymer brushes of PEG and PCL have been synthesized on the surface of magnetic silica nanoparticles using “grafting to” and “grafting from” techniques. The ratio between the Mw of each polymer defines the polymer segregation on the surface as well as the colloidal stability. When the PEG/PCL ratio is >1, the particles become colloidally stable in aqueous media and can be used as vehicles for high insoluble drugs.

  11. Highlights

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      Photoinitiated atom transfer radical polymerization: Current status and future perspectives

      Sajjad Dadashi-Silab, Mehmet Atilla Tasdelen and Yusuf Yagci

      Article first published online: 6 AUG 2014 | DOI: 10.1002/pola.27327

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      For environmental and practical issues, various initiation techniques involving in situ generation of Cu(I) have been reported to accomplish atom transfer radical polymerization (ATRP) in more realistic condition. The required Cu(I) catalyst for the ATRP can be generated by several approaches involving chemical, electrochemical, copper-containing nanoparticles, and photochemical redox processes. Considering the extensive applications of the process, the photochemically mediated ATRP bring several distinct advantages, including temporal and spatial controls, rapid and energy efficient activation.

  12. Articles

    1. Cationic polymerization of a novel oxetane carrying ionic liquid structure and properties of the obtained poly(ionic liquid)

      Kozo Matsumoto, Tomoaki Chijiiwa and Takeshi Endo

      Article first published online: 6 AUG 2014 | DOI: 10.1002/pola.27342

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      An ionic liquid having an oxetanyl group (OXImTFSI) was synthesized and cationically polymerized. The obtained poly(ionic liquid), polyOXImTFSI, showed high thermal stability, low glass transition temperature, and ionic conductivity.

    2. Synthesis of alkyl-modified poly(sodium glutamate)s for preparation of polymer-protein nanoparticles in combination with N,N,N-trimethyl chitosan

      David Pahovnik, Milijana Grujić, Mateja Cegnar, Janez Kerč and Ema Žagar

      Article first published online: 6 AUG 2014 | DOI: 10.1002/pola.27341

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      A series of hydrophobically modified, negatively charged, water-soluble poly(sodium glutamate)s with different content of octyl grafts were synthesized and used in combination with oppositely charged N,N,N-trimethyl chitosan (TMC) for the preparation of GCSF protein nanoparticles (NPs) by polyelectrolyte complexation method. The effects of degree of poly(sodium glutamate)'s hydrophobic modification and specific preparation conditions on the association efficiency (AE) and final loading of protein in the complexes were studied. The results reveal that, beside electrostatic interaction, the hydrophobic grafts on poly(sodium glutamate)s significantly contribute to AE with GCSF protein, whereas subsequently added TMC solution results in formation of much more defined NPs.

    3. Synthesis and characterization of isoindigo-based polymers using CH-arylation polycondensation reactions for organic photovoltaics

      Walaa Elsawy, Hongkyu Kang, Kilho Yu, Ahmed Elbarbary, Kwanghee Lee and Jae-Suk Lee

      Article first published online: 6 AUG 2014 | DOI: 10.1002/pola.27328

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      A series of three new low bandgap donor–acceptor–donor–acceptor/(D–A–D–A/) polymers have been successfully synthesized for photovoltaic application, based on the combination of isoindigo as the electron-deficient acceptor and 3,4-ethylenedioxythiophene as the electron-rich donor, followed by CH-arylation with different acceptors (4,7-dibromo[c][1,2,5]-(oxa, thia and/or selena)diazole(4a-c)).

    4. One-pot synthesis of linear- and three-arm star-tetrablock quarterpolymers via sequential metal-free ring-opening polymerization using a “catalyst switch” strategy

      Junpeng Zhao, David Pahovnik, Yves Gnanou and Nikos Hadjichristidis

      Article first published online: 6 AUG 2014 | DOI: 10.1002/pola.27332

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      Two epoxides (1,2-butylene oxide and ethylene oxide) were successively polymerized from a monohydroxy or trihydroxy initiator using a strong phosphazene base promoter. An excess of diphenyl phosphate was introduced, followed by successive addition and polymerization of a cyclic carbonate (trimethylene carbonate) and a cyclic ester (δ-valerolactone or ε-caprolactone). Linear- and star-tetrablock quarterpolymers were prepared in one pot using this “catalyst switch” strategy.

  13. Rapid Communication

    1. Aspect ratio effect of nanorod surfactants on the shape and internal morphology of block copolymer particles

      Kang Hee Ku, Hyunseung Yang, Jae Man Shin and Bumjoon J. Kim

      Article first published online: 6 AUG 2014 | DOI: 10.1002/pola.27333

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      The effect of aspect ratio (AR) of nanorod (NR) surfactants on the shape and internal morphology of block copolymer (BCP) particles was systemically investigated using CuPt NRs with different AR values ranging from 1 to 15. The positioning of the NRs in the BCP particles was dependent strongly on their AR values, and it enabled the modulation of the interfacial properties at selective locations on the BCP particles, thus producing interesting morphological transition of the BCP particles.

  14. Articles

    1. Hydroxyfunctional oxetane-inimers with varied polarity for the synthesis of hyperbranched polyether polyols via cationic ROP

      Eva-Maria Christ, Sophie S. Müller, Elena Berger-Nicoletti and Holger Frey

      Article first published online: 1 AUG 2014 | DOI: 10.1002/pola.27315

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      Hydroxyl-functionalized oxetane-inimers with varied alkyl chain length—3-hydroxymethyl-3-methoxymethyloxetane, 3-hydroxymethyl-3-propoxymethyloxetane, and 3-hexoxymethyl-3-hydroxymethyloxetane—were synthesized. Cationic ring-opening polymerization leads to hyperbranched polymers with degrees of branching between 34 and 69%. Via polymerization with 1,1,1-tris(4-hydroxyphenyl)ethane under slow monomer addition conditions, high apparent molecular weights up to 11,220  g  mol−1 were obtained. Glass transition and solubility of the polymers can be tailored by varying the alkyl chain length.

    2. Controlled cyclopolymerization of 4,5-disubstituted 1,7-octadiynes and its application to the synthesis of a dendronized polymer using Grubbs catalyst

      Hyeon Park, Ho-Keun Lee, Eun-Hye Kang and Tae-Lim Choi

      Article first published online: 1 AUG 2014 | DOI: 10.1002/pola.27317

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      Cyclopolymerization of 4,5-disubstituted 1,7-octadiyne using a third generation Grubbs catalyst is reported. With this highly reactive polymerization method, monomers with substituents varying from small ester to large dendron were successfully polymerized with rapid propagation rate.

  15. Rapid Communications

    1. Synthesis and characterization of novel amphiphilic super-H copolymers with linear–dendritic architecture

      Ivan Gitsov, Iliana V. Berlinova and Nikolay G. Vladimirov

      Article first published online: 1 AUG 2014 | DOI: 10.1002/pola.27318

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      Novel linear–dendritic super-H block copolymers are prepared by multistage synthetic process involving “living” polymerizations.

    2. Self-assembly and reassembly of fiber-forming dipeptides for pH-triggered DNA delivery

      Glenn R. Hafenstine, Dylan W. Domaille, Jennifer N. Cha and Andrew P. Goodwin

      Article first published online: 31 JUL 2014 | DOI: 10.1002/pola.27319

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      Hydrazone-based conjugates of PEG-dipeptide and DNA-dipeptide were designed to form stable vesicles at neutral pH, break apart at mildly acidic pH, and form large peptide fibers on release. Light scattering measurements showed that DNA-loaded vesicles of ∼80 nm were stable at pH 7.4 for 6 h and fell apart within 1 h at pH 5, with the DNA fully released from the formed fibers.

  16. Articles

    1. Synthesis and thermal, optical, and mechanical properties of sequence-controlled poly(1-adamantyl acrylate)-block-poly(n-butyl acrylate) containing polar side group

      Yoshinori Nakano, Eriko Sato and Akikazu Matsumoto

      Article first published online: 31 JUL 2014 | DOI: 10.1002/pola.27322

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      Thermal, optical, and mechanical properties of the adamantane-containing block copolymers consisting of poly(1-adamantyl acrylate) and poly(n-butyl acrylate) sequences, prepared by the sequence-controlled block copolymerization using organotellurium-mediated living radical polymerization, are described. The increases in the glass transition temperatures and activation energies due to the formation of intermolecular hydrogen bonding by the introduction of polar repeating units as well as their effects on the tensile elasticity, strength, and strain are discussed.

    2. Bulk dispersion of single-walled carbon nanotubes in silicones using diblock copolymers

      Ryan C. Chadwick, Darryl Fong, Nicole A. Rice, Michael A. Brook and Alex Adronov

      Article first published online: 30 JUL 2014 | DOI: 10.1002/pola.27313

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      Supramolecular complexes of poly(3-decylthiophene)-block-polydimethylsiloxanes (P3DT-b-PDMS) with single-walled carbon nanotubes (SWNTs) enable homogeneous incorporation of SWNTs within a bulk silicone elastomer, resulting in a low percolation threshold. The block copolymer anchors SWNTs within the silicone elastomer, allowing repeated stretching and relaxation without degradation of conductivity.

  17. Highlight

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      Functional aqueous assemblies of linear-dendron hybrids

      Greg Whitton and Elizabeth R. Gillies

      Article first published online: 30 JUL 2014 | DOI: 10.1002/pola.27316

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      Recent progress on the development of aqueous assemblies of linear-dendron hybrids capable of performing functions is described. By engineering chemical functionalities in the linear or dendritic component, as well as their architectures, a wide variety of functions—including drug encapsulation, cell targeting, lectin binding, hydrogel formation, and catalysis—can be introduced. In addition, the assemblies can be designed to respond to a variety of stimuli including pH, temperature, light, and enzymes.

  18. Articles

    1. Effects of polyethylene spacer length in polymeric electrolytes on gelation of ionic liquids and ionogel properties

      Jun'ichi Nagasawa, Sonoko Wakahara, Hajime Matsumoto, Hideyuki Kihara and Masaru Yoshida

      Article first published online: 28 JUL 2014 | DOI: 10.1002/pola.27310

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      Positively charged polyelectrolytes with N,N′ -(trans-cyclohexane-1,4-diyl)dibenzamide linkages and varying spacer lengths have been synthesized and their ability to effect gelation for six ionic liquids and the properties of the resulting ionogels have been examined. The polymers gelatinize most of the tested ionic liquids at low concentrations (0.9-50 g/L). Gel-sol transition temperatures are dependent on the spacer length, while ionic conductivities of the various ionogels are near those of the neat ionic liquids and are not affected by spacer length.

    2. Poling and crosslinking processes in NLO polymers

      William K. Bell, Brandon M. Rawlings, Brian K. Long, R. Chad Webb, B. Keith Keitz, Lukas Häußling and C. Grant Willson

      Article first published online: 25 JUL 2014 | DOI: 10.1002/pola.27298

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      A series of photocrosslinkable nonlinear-optical polymers was synthesized, poled and evaluated on the basis of the thermal stability of Second Harmonic Generation (SHG). Through the use of photoinitiation, greater control over the curing process was realized. Thermal stability increased with crosslinker substitution, and in some cases SHG was maintained well beyond the initial Tg.

    3. Poly(vinylphosphonate)s functionalized polymer microspheres via rare earth metal-mediated group transfer polymerization

      Jiming Yang, Yongjiu Liang, Stephan Salzinger, Ning Zhang, Dewen Dong and Bernhard Rieger

      Article first published online: 25 JUL 2014 | DOI: 10.1002/pola.27324

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      A facile and efficient method is demonstrated for the functionalization of polymer microspheres with biocompatible poly(vinylphosphonate)s via the combination of UV-induced photopolymerization and rare-earth metal catalyzed group transfer polymerization (GTP). The surface-initiated GTP leads to a constant and remarkably rapid weight gain of the microsphere, and the accumulated tension between polymer chains induces an unprecedented fracture of the microsphere for longer polymerization time.

    4. Self-healing of poly(propylene oxide)-polybenzoxazine thermosets by photoinduced coumarine dimerization

      Baris Kiskan and Yusuf Yagci

      Article first published online: 25 JUL 2014 | DOI: 10.1002/pola.27323

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      A self-healing strategy for poly(propylene oxide)s bearing coumarine-benzoxazine units (PPO-CouBenz)s based on light induced coumarine dimerization reactions is described. The coumarine groups present in the structure undergo efficient dimerization upon irradiation at λ > 300 nm as confirmed by the UV–Vis spectral investigations. Photoinduced healing of coumarin based cured PPO-CouBenz polymer films was investigated.

  19. Rapid Communication

    1. You have free access to this content
      Kilogram scale inverse vulcanization of elemental sulfur to prepare high capacity polymer electrodes for Li-S batteries

      Jared J. Griebel, Guoxing Li, Richard S. Glass, Kookheon Char and Jeffrey Pyun

      Article first published online: 25 JUL 2014 | DOI: 10.1002/pola.27314

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      Synthetic conditions to prepare high sulfur content copolymers via inverse vulcanization on a kilogram scale is reported. By investigation of polymerization comonomer feed ratios, reaction temperature, and scale, the development of conditions to enabled the large scale synthesis of poly(sulfur-random-(1,3-diisopropenylbenzene) was conducted. We further demonstrated enhanced device performance of these sulfur copolymers as active cathode materials in Li-S batteries.

  20. Articles

    1. Synthesis of degradable molecular brushes via a combination of ring-opening polymerization and click chemistry

      Yi Shi, Xiaofeng Wang, Robert W. Graff, William A. Phillip and Haifeng Gao

      Article first published online: 23 JUL 2014 | DOI: 10.1002/pola.27307

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      Molecular brushes with an acid-degradable backbone and densely-grafted side chains (2 side chains per backbone repeating unit) are synthesized using an efficient grafting-onto method. The incorporated side chains vary from homopolymers to block copolymers and grafted polymers, and the produced molecular brushes can be degraded completely into linear polymers. When a mixture of side chains are used, the amphiphilic hetero-grafted molecular brushes can assemble in water and form either spherical micelles or hollow vesicles depending on sample compositions.

    2. Synthesis and photoluminescence behaviors of anthracene-layered polymers

      Yasuhiro Morisaki, Tatsuya Nakano and Yoshiki Chujo

      Article first published online: 23 JUL 2014 | DOI: 10.1002/pola.27306

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      Aromatic-ring layered polymers consisting of layered anthracenes and fluorescence quenchers at the polymer chain-ends are designed and synthesized. Photoluminescence behaviors show that the polymers act as single molecular wires.

    3. Postpolymerization modification of reactive polymers derived from vinylcyclopropane. III. Polymer sequential functionalization using a combination of amines with alkoxyamines, hydrazides, isocyanates, or acyl halides

      Denis Hervé Seuyep Ntoukam, Gerrit Albert Luinstra and Patrick Theato

      Article first published online: 23 JUL 2014 | DOI: 10.1002/pola.27311

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      1,1-Disubtitutedvinylcyclopropane were used to prepare a polymer with two readily functionalizable side chain consisted of pentaflourophenyl and ketone. Sequential post-modification was successfully performed and a library of double functional polymers was prepared with a precise positioning of the functionality in the polymer backbone.

    4. Anionic alternating copolymerization of α-arylacrylates with methyl methacrylate: Effect of monomer sequence on fluorescence

      Yasuhiro Kohsaka, Eiji Yamaguchi and Tatsuki Kitayama

      Article first published online: 22 JUL 2014 | DOI: 10.1002/pola.27305

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      Anionic polymerizations of acrylates possessing various aromatic fluorophores in α-substituents were investigated as well as the properties of the obtained polymers. Copolymerization of α-(2-naphthyl)acrylate and α-(2-fluorenyl)acrylate with methyl methacrylate (MMA) afforded alternating copolymers. Although the homopolymer of α-(2-fluorenyl)acrylate exhibited strong excimer emission in diluted chloroform solution, strong monomer emission was observed from the corresponding alternating copolymer, demonstrating the sequence-control effect on the emission properties.

    5. Control of microstructure and gradient property of polymer network by photopolymerizable silicone-containing nanogel

      Cong Chen, JianCheng Liu, Fang Sun and Jeffrey W. Stansbury

      Article first published online: 22 JUL 2014 | DOI: 10.1002/pola.27309

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      The silicone-containing nanogel with self-floating ability can not only reduce polymerization stress, but also spontaneously form a gradient distribution of concentration, leading to a gradient change in the thermal stability of the polymer and a more hydrophobic surface with altered surface microstructure.

    6. Facile synthesis of high-molecular-weight acid-labile polypeptides using urethane derivatives

      Shirley Wong and Young Jik Kwon

      Article first published online: 22 JUL 2014 | DOI: 10.1002/pola.27320

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      Preparation of acid-labile polypeptides by conventional methods, which polymerize unstable, moisture-sensitive amino acid monomers under highly restrictive conditions, has been challenging. A new method is reported that allows convenient synthesis of stable monomers and fast polymerization under easily applicable conditions, yielding high-molecular-weight acid-labile polypeptides with narrow polydispersity. The highly facile strategy demonstrated in this study could contribute to synthesizing stimuli-responsive peptide-based biomaterials for various biomedical applications.

    7. Synthetic control over the dynamics of mesoscaled cargo release from colloidal polymer vectors inside live cells

      Harvind S. Chahal, Dev S. Chahal, Patrick M. McBride and Brett A. Helms

      Article first published online: 22 JUL 2014 | DOI: 10.1002/pola.27312

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      Dynamic complementarity between colloidal polymer vectors and their electrostatically adsorbed cargo is a critical parameter that influences the rate of cargo release once inside cells. Where endogenous macromolecules within the cytosol favorably compete for adsorption sites at the vector surface, cargo can be efficiently released and trafficked to intracytosolic targets.

    8. A combining signal amplification of atom transfer radical polymerization and redox polymerization for visual biomolecules detection

      Dequan Zhuang, Heyun Shen, Guodong Liu, Changyuan Yu and Jing Yang

      Article first published online: 22 JUL 2014 | DOI: 10.1002/pola.27303

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      Ce4+ as oxidant of redox polymerization directly combined with the hydroxyl groups generated from atom transfer radical polymerization to realize visual signal amplification.

    9. Synthesis of brush-shaped polymers consisting of a poly(phenylacetylene) backbone and pendant poly(vinyl ether)s via selective reaction of 2-Vinyloxyethyl 4-Ethynylbenzoate

      Jin Motoyanagi, Kiriko Higashi and Masahiko Minoda

      Article first published online: 20 JUL 2014 | DOI: 10.1002/pola.27304

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      A bifunctional monomer (PAVE) containing both a phenylacetylene (PA) group and a vinyl ether (VE) group was designed for the synthesis of π-conjugated brush-shaped polymers. First, polyVE-based macromonomers consisting of a PA group at the terminus were synthesized via living cationic polymerization using a trifluoroacetic acid adduct of PAVE as an initiator, and then polymerized with Rh catalysis to afford brush-shaped polymers consisting of a polyPA backbone and pendant polyVEs.

    10. Surface patterned graft copolymerization of hydrophilic monomers onto hydrophobic polymer film upon UV irradiation

      Ryusuke Enomoto, Masanao Sato, Shota Fujii, Tomoyasu Hirai, Atsushi Takahara, Kazuhiko Ishihara and Shin-ichi Yusa

      Article first published online: 20 JUL 2014 | DOI: 10.1002/pola.27308

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      A random copolymer [p(MMA/DMAB)] composed of MMA and 2,2-dimethoxy-1,2-di(4-methacryloyloxy)phenylethane-1-one (DMAB) was prepared by free radical random copolymerization. A hydrophobic polymer film was then prepared from p(MMA/DMAB). Hydrophilic 2-methacryloyloxyethyl phosphorylcholine (MPC) was graft-copolymerized from the hydrophobic film in water by photo-cleavage of the DMAB unit. MPC can be grafted onto the surface of the film selectively at UV-irradiated sites.

    11. High-performance segmented polyurea by transesterification of diphenyl carbonates with aliphatic diamines

      Wen Chen Pan, Ching-Hsuan Lin and Shenghong A. Dai

      Article first published online: 15 JUL 2014 | DOI: 10.1002/pola.27302

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      A new process has succeeded in synthesizing segmented polyurea elastomers through diphenyl carbonate and aliphatic diamines in the absence of isocyanates. The new SPUaE products not only possess distinctive segmented properties but also show high thermal stabilities and mechanical performances. The most optimized polyurea films made in this study has the ηinh of 0.64, tensile strength of greater than 30 MPa, and elongation exceeding 400% with thermal stability higher than 280 °C. Thus, this new green synthetic methodology could provide the industries with a safer alternative way to develop new SPUaE.

    12. Synthesis and characterization of double hydrophilic block copolymers containing semi-rigid and flexible segments

      Alice M. Savage, Elizabeth Ullrich, Stacey M. Chin, Zachary Kiernan, Caitlyn Kost and S. Richard Turner

      Article first published online: 15 JUL 2014 | DOI: 10.1002/pola.27296

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      Two sterically crowded stilbene comonomers, 3-methyl-(E)-stilbene (3MSti) and 4-(diethylamino)-(E)-stilbene, are polymerized separately with maleic anhydride using reversible addition-fragmentation chain transfer (RAFT) polymerization techniques. RAFT agent compatibilities and reaction kinetics for each comonomer system are compared. Double hydrophilic block copolymers are synthesized from these copolymers and converted to polyelectrolytes. The isoelectric point and dissociation behavior of the polyelectrolytes are determined using ζ-potential and acid-base titrations, respectively.

    13. Siloxane-mediated ethylene oligomerization with iron-based catalysts: Retarding the polymer formation

      Jian Ye, Binbo Jiang, Jingdai Wang, Yongrong Yang and Qun Pu

      Article first published online: 15 JUL 2014 | DOI: 10.1002/pola.27295

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      Simultaneous production of undesired insoluble polymers during ethylene oligomerization is a potential obstacle for bis(imino)pyridine iron catalysts to commercialization. An effective strategy is detailed for retarding the polymer formation by introducing siloxanes as modifiers into such systems. The influence of siloxanes could be a comprehensive result of their interactions with the catalytic components, through the modulation on both the electronic and steric effects of the active centers.

    14. A novel solventless coating method to graft low-molecular weight polyethyleneimine on silica fine powders

      Nerea Murillo-Cremaes, Pedro López-Aranguren, Lourdes F. Vega, Javier Saurina, Anna Roig and Concepción Domingo

      Article first published online: 15 JUL 2014 | DOI: 10.1002/pola.27297

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      A ring-opening polymerization process catalyzed by compressed CO2 at low pressure and temperature and in the absence of any organic solvent is presented. Designed to fabricate hybrid materials involving two types of silica nanoparticles (one of them with a magnetic core) coated with hyperbranched polyethyleneimine of low molecular weight, the process resulted in an ideal candidate material for several biomedical applications.

    15. Advances in the frontal ring opening metathesis polymerization of dicyclopentadiene

      Andrea Ruiu, Davide Sanna, Valeria Alzari, Daniele Nuvoli and Alberto Mariani

      Article first published online: 15 JUL 2014 | DOI: 10.1002/pola.27301

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      Recent developments of Grubbs' catalysts and their inhibitors are exploited in order to successfully couple frontal polymerization to the ring opening metathesis polymerization of dicyclopentadiene. The molar catalysts to monomer and catalysts to inhibitor ratios that allow achieving a pure frontal polymerization and sufficiently long pot lives are determined. Polydicyclopentadiene is obtained in quantitative yields and short times.

    16. Selective interactions of a high-molecular-weight polycarbazole with different commercial nanotube samples

      Nicole A. Rice and Alex Adronov

      Article first published online: 9 JUL 2014 | DOI: 10.1002/pola.27292

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      The interaction of a high molecular weight polycarbazole with single-walled carbon nanotubes (SWNTs) was found to be selective for semiconducting SWNTs. This polymer was able to disperse commercial raw HiPCO, purified HiPCO, and CoMoCat SWNTs. Annealing of the purified HiPCO SWNTs led to a dramatic improvement of spectroscopic properties

    17. ABA triblock copolymers from two mechanistic techniques: Polycondensation and atom transfer radical polymerization

      Natalia A. Agudelo, Andrea M. Elsen, Hongkun He, Betty L. López and Krzysztof Matyjaszewski

      Article first published online: 9 JUL 2014 | DOI: 10.1002/pola.27300

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      A series of ABA triblock copolymers were synthesized utilizing two polymerization techniques, polycondensation and atom transfer radical polymerization (ATRP). The choice of polymerization mechanisms results in block copolymers with unique molecular weight distributions the center of these triblock copolymers are disperse, resulting from polycondensation while the outside blocks have narrow molecular weight distribution due to the control afforded from ATRP.

    18. Synthesis and self-assembly of thermosensitive double-hydrophilic poly(N-vinylcaprolactam)-b-poly(N-vinyl-2-pyrrolidone) diblock copolymers

      Xing Liang, Veronika Kozlovskaya, Christopher P. Cox, Yun Wang, Mohammad Saeed and Eugenia Kharlampieva

      Article first published online: 4 JUL 2014 | DOI: 10.1002/pola.27291

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      Novel temperature-responsive double-hydrophilic poly(N-vinylcaprolactam)-b-poly(N-vinyl-2-pyrrolidone) (PVCL-b-PVPON) diblock copolymers are synthesized through the reversible addition-fragmentation chain transfer polymerization. The copolymers became amphiphilic upon heating due to the reversible coil-to-globule transition of PVCL blocks. Remarkably, the PVCL-b-PVPON copolymers perform temperature-induced self-assembly into nanostructures from 70 nm to 200 nm in size with the hydrophobic PVCL blocks shielded by hydrophilic PVPON blocks.

    19. Well-controlled RAFT polymerization initiated by recyclable surface-modified Nb(OH)5 nanoparticles under visible light irradiation

      Jizhen Zhang, Aihua Li, Huihui Liu, Dongjiang Yang and Jingquan Liu

      Article first published online: 23 JUN 2014 | DOI: 10.1002/pola.27288

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      A recyclable solid-state photoinitiator based on the surface modified niobium hydroxide was prepared and successfully introduced into RAFT polymerization under visible light illumination. It is revealed that well-defined polymers with controlled molecular weight and narrow PDI can be achieved and the polymerization is highly responsive to light initiation. In addition, the photoinitiator can be recycled and reused to initiate the polymerization for many times without significant decrease of initiation efficiency.

  21. Highlight

    1. Optimization of direct arylation polymerization (DArP) through the identification and control of defects in polymer structure

      Andrey E. Rudenko and Barry C. Thompson

      Article first published online: 20 JUN 2014 | DOI: 10.1002/pola.27279

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      Just like any other method of polymerization, direct arylation polymerization (DArP) produces defects in polymer structure, which have a strong impact on polymer properties. Therefore, it is important for polymer scientists to understand what causes the defect formation and how to control them. DArP produces four major classes of defects, and here we discuss in detail the origin of defects, their influence on polymer properties and the available methods to control them.

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