Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 53 Issue 19

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

Impact Factor: 3.113

ISI Journal Citation Reports © Ranking: 2014: 18/82 (Polymer Science)

Online ISSN: 1099-0518

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

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  1. 1 - 98
  1. Articles

    1. Continuous flow synthesis of poly(methyl methacrylate) via a light-mediated controlled radical polymerization

      Anna Melker, Brett P. Fors, Craig J. Hawker and Justin E. Poelma

      Article first published online: 29 AUG 2015 | DOI: 10.1002/pola.27765

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      Recently, the ability to control polymerizations using external stimuli such as light has gained attention. However, scaling up these reactions presents unique challenges such as shallow and uneven penetration of light through the reaction medium, effectively lowering the rate of polymerization. To circumvent these issues, a continuous flow reactor was used with special attention made to choice of tubing material, yielding 50% faster reaction rates compared to batch reactions.

    2. Polyisobutylene-based polyurethanes: VII. structure/property investigations for medical applications

      Kalman Toth, Nihan Nugay and Joseph P. Kennedy

      Article first published online: 28 AUG 2015 | DOI: 10.1002/pola.27804

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      The hydrolytic, oxidative, and metal ion oxidative resistance of PIB-based polyurethane is far superior to that of PDMS-based commercial polyurethane (Elast-Eon™ E2A), while their static mechanical properties (tensile strength and elongation) are comparable.

    3. High molecular weight and low dispersity polyacrylonitrile by low temperature RAFT polymerization

      Jeremy D. Moskowitz, Brooks A. Abel, Charles L. McCormick and Jeffrey S. Wiggins

      Article first published online: 28 AUG 2015 | DOI: 10.1002/pola.27806

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      Well-controlled polymers with uniform dispersity and high molecular weight serve as excellent model precursors for further study of in situ carbon fiber production of PAN-based carbon fibers. Well-controlled high molecular weight and low dispersity polyacrylonitrile (PAN) was synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. Through low temperature (30 °C) RAFT polymerization, chain termination and chain transfer reactions were suppressed leading to improved control, higher molecular weight PAN, and higher conversions.

    4. Effect of multiple H-bonding on the properties of polyimides containing the rigid rod groups

      Xiaoye Ma, Chuanqing Kang, Wenhui Chen, Rizhe Jin, Haiquan Guo, Xuepeng Qiu and Lianxun Gao

      Article first published online: 28 AUG 2015 | DOI: 10.1002/pola.27808

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      Five fully symmetrical diamines containing benzimidazole, benzoxazole, and hydroxyl group were synthesized and a series of polyimides were prepared by the reaction of these diamines with commercial aromatic dianhydrides. The influence on the properties of PIs by the introduction of rigid rod-like nitrogen heterocyclic structure and the formation of intra-/intermolecular H-bonding has been discussed.

    5. Radical polymerization behavior and molecular weight development of homologous monoacrylate monomers in lyotropic liquid crystal phases

      Michael A. DePierro, Céline Baguenard and C. Allan Guymon

      Article first published online: 27 AUG 2015 | DOI: 10.1002/pola.27783

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      Surfactant self-assembly can generate lyotropic liquid-crystalline mesophases such as hexagonal, bicontinuous cubic, or lamellar nanostructures. These geometries can be used as a photopolymerization template to synthesize materials with nanoscale features. Rapid radical polymerization kinetics and thermodynamics are key factors to better control nanostructure retention. Herein, monomer polarity, light intensity, and template geometry are correlated to the evolution of polymer molecular weight and radical photopolymerization kinetics to better understand the parameters that can improve the nanostructure transfer.

    6. Synthesis of poly(n-butyl acrylate) homopolymer and poly(styrene-b-n-butyl acrylate-b-styrene) triblock copolymer via AGET emulsion ATRP using a cationic surfactant

      Zhigang Xue, Zhen Wang, Dan He, Xingping Zhou and Xiaolin Xie

      Article first published online: 27 AUG 2015 | DOI: 10.1002/pola.27809

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      The AGET emulsion ATRPs using cationic surfactants are reported. Most of the systems showed the typical features of controlled radical polymerization.

    7. Homopolymerization and copolymerization kinetics of trimethylene carbonate bearing a methoxyethoxy side group

      Fei Chen and Brian G. Amsden

      Article first published online: 27 AUG 2015 | DOI: 10.1002/pola.27805

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      The homo- and copolymerization kinetics of a functional cyclic carbonate monomer bearing a methoxyethoxy pendant group (TMCM-MOE3OM) was investigated using the organocatalyst DBU as well as metal catalyst Sn(Oct)2. Compared with non-functionalized TMC as well as LLA, ring-chain equilibrium and autopolymerization were observed in the polymerization of TMCM-MOE3OM with either catalyst. This equilibrium along with autopolymeriation resulted in the formation of oligomers with Mn lower than 5000 Da.

    8. Sulfonated dendrimer- and hyperbranched polyglycerol-PBIOO® blend membranes for fuel cells

      Manuela Martín-Zarco, Joaquín C. García-Martínez and Julián Rodríguez-López

      Article first published online: 22 AUG 2015 | DOI: 10.1002/pola.27777

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      Acid-base proton-conducting membranes were prepared by blending either a new sulfonated dendrimer or different sulfonated hyperbranched polyglycerols with PBIOO®. Proton exchange capacity, water uptake, thermal stability, and proton conductivity were strongly dependent on the molecular structure and the microphase separation in the membranes.

    9. Synthesis and photovoltaic properties of 2,6-bis(2-thienyl) benzobisazole and 4,8-bis(thienyl)-benzo[1,2-B:4,5-B′]dithiophene copolymers

      Achala Bhuwalka, Monique D. Ewan, Moneim Elshobaki, Jared F. Mike, Brian Tlach, Sumit Chaudhary and Malika Jeffries-EL

      Article first published online: 22 AUG 2015 | DOI: 10.1002/pola.27793

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      Three donor–acceptor copolymers based on a donor–acceptor–donor triad of cis-benzbisoxazole, trans-benzobisoxazole, or trans-benzobisthiazole, and 4,8-bis(5-(2-ethylhexyl)-thien-2-yl)-benzo[1,2-b:4,5-b′]dithiophene were synthesized and the impact of these structural modifications the optical, electrochemical, and morphological properties of the polymers investigated. The performance of these copolymers in photovoltaic cells is also reported.

    10. Synthesis of an esterase-sensitive degradable polyester as facile drug carrier for cancer therapy

      Zhuxian Zhou, William J. Murdoch and Youqing Shen

      Article first published online: 22 AUG 2015 | DOI: 10.1002/pola.27798

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      The esterase-sensitive degradable polyether-based drug carrier (PEGx) was synthesized by polycondensation of PEG400 and dianhydride (A) following with conjugation of PEG2000 (B). Anticancer drugs were loaded by covalent conjugation through multiple carboxyl acid groups on PEGx and this polymer drug conjugates exhibited esterase-promoted degradation and drug release (C).

    11. Synthesis and characterization of new low band-gap polymers containing electron-accepting acenaphtho[1,2-c]thiophene-S,S-dioxide groups

      Yu-Rim Shin, Woo-Hyung Lee, Jong Baek Park, Ji-Hoon Kim, Sang Kyu Lee, Won Suk Shin, Do-Hoon Hwang and In-Nam Kang

      Article first published online: 21 AUG 2015 | DOI: 10.1002/pola.27797

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      Syntheses and characterization of two new acenaphthothiophene-S, S-dioxide (TSSO-based donor–acceptor polymers were described. The incorporation of TSSO units in these D–A polymers reduces their optical band-gap and HOMO/LUMO energy levels to produce a low band-gap polymer, which indicates the TSSO unit acts as a good electron-accepting unit in D–A donor polymer systems.

    12. End-functionalized polylactides using a calcium-based precatalyst: Synthesis and insights by mass spectrometry

      Ilknur Yildirim, Sarah Crotty, Claas H. Loh, Grit Festag, Christine Weber, Pier-Francesco Caponi, Michael Gottschaldt, Matthias Westerhausen and Ulrich S. Schubert

      Article first published online: 21 AUG 2015 | DOI: 10.1002/pola.27795

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      End-functionalized PLAs via ring opening polymerization of l-lactide were synthesized with heavy metal free catalysis. A variety of alcohols was used as initiator precursors like primary, secondary as well as tertiary alcohols. This enabled the direct introduction of targeting moieties, a drug molecule, a fluorescent label and a raft agent. All PLAs have been intensively investigated by mass spectrometry besides SEC and NMR spectroscopy.

    13. A route toward multifunctional polyurethanes using triple click reactions

      Erhan Demirel, Hakan Durmaz, Gurkan Hizal and Umit Tunca

      Article first published online: 17 AUG 2015 | DOI: 10.1002/pola.27796

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      The aliphatic polyurethane, with pendant alkyne, perfluorophenyl, and anthracene moieties, was prepared from polycondensation of anthracene, alkyne, and perfluorophenyl functional-diols with hexamethylenediisocyanate in the presence of dibutyltindilaurate in CH2Cl2 at room temperature for 10 days. Thereafter, the PU-(anthracene-co-alkyne-co-perfluorophenyl) (Mn,GPC = 15,600 g/mol, Mw/Mn = 1.37, relative to PS standards) was sequentially clicked with benzyl azide, octylamine, and 4-(2-hydroxyethyl)−10-oxa-4-azatricyclo[5.2.1.02,6]dec-8-ene-3,5-dione (adduct alcohol) via copper-catalyzed azide-alkyne cycloaddition, active ester substitution, and Diels–Alder reactions, respectively, to finally yield PU-(hydroxyl-co-benzyltriazole-co-octylamine).

    14. Synthesis of poly(ethylene-co-vinyl alcohol)-g-polystyrene graft copolymer and their applications for ordered porous film and compatibilizer

      Haotian Wu, Tao Jiang, Jun Zhu, Kun Cui, Qiaoling Zhao and Zhi Ma

      Article first published online: 17 AUG 2015 | DOI: 10.1002/pola.27799

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      A series of poly(ethylene-co-vinyl alcohol)-g-polystyrene graft copolymers (EVAL-g-PS) were synthesized via the combination of the hydrolysis of poly(ethylene-co-vinyl acetate), the transformation of hydroxyl on the side chain through esterification and the ATRP of polystyrene. The applications of the copolymers in fabricating ordered porous films and compatibilizer for the blend system of low-density polyethylene/polystyrene are observed by SEM.

    15. Silicon-based mercaptans: High-performance monomers for thiol-ene photopolymerization

      Meinhart Roth, Andreas Oesterreicher, Florian H. Mostegel, Andreas Moser, Gerald Pinter, Matthias Edler, Richard Piock and Thomas Griesser

      Article first published online: 17 AUG 2015 | DOI: 10.1002/pola.27792

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      Ester-free silicon-based thiol monomers were successfully synthesized and evaluated for an application in thiol-ene resins. Polymerization reaction rates, conversion, network properties, shelf-life as well as degradation experiments of those thiol monomers in combination with triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione were performed and compared with formulations containing pentaerythritol tetra-3-mercaptopropionate. Kinetic analysis revealed appropriate reaction rates and conversions reaching 90% and higher. The excellent degradation resistance of photocured silane-based formulations makes these multifunctional mercaptans interesting candidates for high-performance applications.

    16. Novel reversible thermoresponsive nanogel based on poly(ionic liquid)s prepared via RAFT crosslinking copolymerization

      Yong Zuo, Na Guo, Zhenqian Jiao, Pengfei Song, Xiaojun Liu, Rongmin Wang and Yubing Xiong

      Article first published online: 17 AUG 2015 | DOI: 10.1002/pola.27789

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      In this study, a facile strategy for the preparation of thermo- and pH-responsive nanogels based on ionic liquids is fabricated through the reversible addition-fragmentation transfer (RAFT) cross-linking copolymerization in selective solvents. The use of chain transfer agents containing carboxyl groups in the RAFT polymerizations is the key to producing highly thermoresponsive nanogels. Furthermore, these nanogels can be further decorated via surface-grafting polymerization.

    17. Allyl sulfides and α-substituted acrylates as addition–fragmentation chain transfer agents for methacrylate polymer networks

      Samuel Clark Ligon, Konstanze Seidler, Christian Gorsche, Markus Griesser, Norbert Moszner and Robert Liska

      Article first published online: 17 AUG 2015 | DOI: 10.1002/pola.27788

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      Allyl sulfide and α-substituted acrylate based addition–fragmentation chain transfer agents can effectively modify the rate of gelation of multifunctional methacrylate monomers. Shrinkage stress is reduced and mechanical properties of the resultant network are positively influenced.

  2. Highlights

    1. Copper and iron complexes as visible-light-sensitive photoinitiators of polymerization

      Pu Xiao, Jing Zhang, Damien Campolo, Frederic Dumur, Didier Gigmes, Jean Pierre Fouassier and Jacques Lalevée

      Article first published online: 14 AUG 2015 | DOI: 10.1002/pola.27762

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      Copper or iron complexes with well-designed ligands can be utilized as photoinitiators of various polymerization reactions such as free radical photopolymerization, cationic photopolymerization, thiol-ene photopolymerization, and controlled radical photopolymerization under irradiation of visible light. The high efficiency and low cost of these complexes may endow them with potential applications in fabrication of polymer materials in green chemistry circumstance.

  3. Articles

    1. In situ fabrication of paclitaxel-loaded core-crosslinked micelles via thiol-ene “click” chemistry for reduction-responsive drug release

      Ying Huang, Rui Sun, Qiaojie Luo, Ying Wang, Kai Zhang, Xuliang Deng, Weipu Zhu, Xiaodong Li and Zhiquan Shen

      Article first published online: 11 AUG 2015 | DOI: 10.1002/pola.27778

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      A facile method to fabricate reduction-responsive core-crosslinked paclitaxel-loaded micelles via in situ thiolene “click” reaction is reported. These micelles could quickly release paclitaxel in response to high glutathione concentration in tumor cells.

    2. Efficient water-soluble drag reducing star polymers with improved mechanical stability

      David P. Cole, Ezat Khosravi and Osama M. Musa

      Article first published online: 11 AUG 2015 | DOI: 10.1002/pola.27779

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      The addition of high-molecular-weight polymers have been shown to greatly reduce the drag experienced by a fluid as it moves through a pipe. These polymers are highly susceptible to mechanical degradation in pipe flow, reducing their efficacy. This work here describes the synthesis of water soluble high-molecular-weight 4-arm star polymers via Cu(0)-mediated controlled radical polymerization. These star polymers demonstrated greatly enhanced mechanical stability in comparison with the currently used commercial polymers.

    3. Synthesis and FET characterization of novel ambipolar and low-bandgap naphthalene-diimide-based semiconducting polymers

      Seijiro Fukuta, Hung-Chin Wu, Tomoyuki Koganezawa, Yukou Isshiki, Mitsuru Ueda, Wen-Chang Chen and Tomoya Higashihara

      Article first published online: 11 AUG 2015 | DOI: 10.1002/pola.27782

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      Naphthalene-diimide-based semiconducting polymers (P1–P4) were synthesized for ambipolar semiconducting materials with near infra-red absorption. The introduction of the thiophene spacer and strongly electron-donating unit successfully extended the absorption peaks up to 1066 nm. P4 showed high electron mobility of 1.5 × 10−2 cmV−1 s−1 and moderate hole mobility of 2.9 × 10−4 cmV−1 s−1.

    4. New alternating D–A1–D–A2 copolymer containing two electron-deficient moieties based on benzothiadiazole and 9-(2-Octyldodecyl)-8H-pyrrolo[3,4-b]bisthieno[2,3-f:3',2'-h]quinoxaline-8,10(9H)-dione for efficient polymer solar cells

      M. L. Keshtov, S. A. Kuklin, D. Y. Godovsky, A. R. Khokhlov, R. Kurchania, F. C. Chen, Emmanuel N. Koukaras and G. D. Sharma

      Article first published online: 11 AUG 2015 | DOI: 10.1002/pola.27786

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      A novel D–A1–D–A2 copolymer P1 containing two electron withdrawing units based on benzothiadiazole (BT) and 9-(2-octyldodecyl)−8H-pyrrolo[3,4-b] bisthieno[2,3-f:3′, 2′-h]quinoxaline-8,10(9H)-dione (PTQD) units was synthesized and used as donor for the fabrication of bulk heterojunction polymer solar cells. The polymer solar cell with optimized P1:PC71BM active layer processed with DIO/CB showed power conversion efficiency of 6.21%.

    5. Synthesis of well-defined star-shaped poly(ε-caprolactone)/poly(ethylbene glycol) amphiphilic conetworks by combination of ring opening polymerization and “click” chemistry

      Cui-Wei Wang, Chao Liu, Xiao-Wei Zhu, Zi-Ying Yang, Hong-Fan Sun, De-Ling Kong and Jing Yang

      Article first published online: 11 AUG 2015 | DOI: 10.1002/pola.27790

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      Star-shaped PCL-PEG amphiphilic conetworks (APCNs) have been synthesized via the combination of ring opening polymerization (ROP) and click chemistry. The APCNs showed different swelling behaviors in different solvent. Furthermore, by in vitro release of hydrophobic and hydrophilic drugs, the APCNs was confirmed to be promising drug depot materials for the hydrophobic and hydrophilic drugs.

  4. Rapid Communication

    1. You have free access to this content
      Hydrothermal synthesis of aromatic polyimide particles by using reaction-induced crystallization

      Daisaku Shojo, Shinichi Yamazaki and Kunio Kimura

      Article first published online: 11 AUG 2015 | DOI: 10.1002/pola.27791

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      Highly crystalline poly(p-phenylene pyromellitimide) plate-like crystals were obtained in water at 280 °C only for 10 min by the combination of the crystallization of oligomers and subsequent polymerization in the crystals. This result provided a new environmentally benign procedure for the preparation of aromatic polyimide particles.

  5. Articles

    1. Thermal response of a PVCL–HA conjugate

      Jukka Niskanen, Mikko Karesoja, Vladimir Aseyev, Xing-Ping Qiu, Françoise M. Winnik and Heikki Tenhu

      Article first published online: 11 AUG 2015 | DOI: 10.1002/pola.27794

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      Diblock copolymers consisting of hyaluronic acid, HA, and poly(N-vinylcaprolactam), PVCL, have been synthesized. The blocks were first end functionalized and then coupled with click chemistry. The HA block consisted of 16–18 saccharide units and the PVCL block of ∼25 repeating units. HA-PVCL conjugate self-assembles in water upon heating into monodisperse, colloidally stable, hollow spherical particles whose size may be tuned with the heating rate of the solution.

    2. Synthesis of poly(arylene ether ketone)s bearing skeletal crown ether units for cation exchange membranes

      Bram Zoetebier, Sinem Tas, G. Julius Vancso, Kitty Nijmeijer and Mark A. Hempenius

      Article first published online: 9 AUG 2015 | DOI: 10.1002/pola.27752

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      Crown ether incorporation into the main chain of poly(arylene ether ketone)s turns these polymers into attractive membrane materials because of their potential ion selectivity. Hydroxy-functionalized dibenzo-18-crown-6 is used as monomer in step growth polymerization to form crown ether-bearing poly(arylene ether ketone)s. Membranes fabricated from sulfonated crown ether-bearing poly(arylene ether ketone)s show a lower potassium ion transport because of crown ether–cation interactions.

    3. Ambiguous anti-fouling surfaces: Facile synthesis by light-mediated radical polymerization

      Christian W. Pester, Justin E. Poelma, Benjaporn Narupai, Shrayesh N. Patel, Gregory M. Su, Thomas E. Mates, Yingdong Luo, Christopher K. Ober, Craig J. Hawker and Edward J. Kramer

      Article first published online: 6 AUG 2015 | DOI: 10.1002/pola.27748

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      Visible light-mediated radical polymerization allows for the fabrication of patterned diblock copolymer brushes. Surface properties of these model hydrophilic/hydrophobic ambiguous diblock brushes composed of anti-fouling relevant monomers were thoroughly characterized, and spatial patterning gives topographically and chemically well-defined surfaces. This strategy combines hydrophilic and hydrophobic properties on the micron length scale. Additionally, advantages of both visible light-mediated photopolymerization and traditional copper-catalyzed atom transfer radical polymerization were combined to achieve both high spatial definition and monomer tolerance.

    4. End group polarity and block symmetry effects on cloud point and hydrodynamic diameter of thermoresponsive block copolymers

      Xu Xiang, Xiaochu Ding, Ning Chen, Beilu Zhang and Patricia A. Heiden

      Article first published online: 6 AUG 2015 | DOI: 10.1002/pola.27757

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      Thermoresponse properties of linear and star block copolymers with 50% hydrophilic oligoethyleneacrylate and 50% more hydrophobic diethyleneglycolmethacrylate were studied for effects of different amphiphilic end groups. The cloud point and temperature range for the coil collapse of linear diblock copolymers were typically more sensitive to the effects of matching polar end groups to the more polar block than the linear triblock or star diblock copolymers. The effects of changing a polar chain end for a more polar chain end were significantly less than the effects of pairing the more polar end group with the more polar block.

    5. Naphthalic anhydride derivatives: Structural effects on their initiating abilities in radical and/or cationic photopolymerizations under visible light

      Pu Xiao, Frédéric Dumur, Jing Zhang, Bernadette Graff, Fabrice Morlet-Savary, Jean Pierre Fouassier, Didier Gigmes and Jacques Lalevée

      Article first published online: 6 AUG 2015 | DOI: 10.1002/pola.27763

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      Naphthalic anhydride derivatives are promising photoinitiators for both the cationic polymerization and the free radical polymerization under blue light or polychromatic visible light. And the substituents in the naphthalic anhydride skeleton significantly affect their relative photoinitiation ability.

    6. Amphiphilic silica/fluoropolymer nanoparticles: Synthesis, tem-responsive and surface properties as protein-resistance coatings

      Hongpu Huang, Jia Qu and Ling He

      Article first published online: 6 AUG 2015 | DOI: 10.1002/pola.27785

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      Amphiphilic nanoparticles of SiO2-g-P(PEGMA)-b-P(12FMA) (150–170 nm) are prepared by SI-ATRP. The introduction of P(12FMA) segments not only provide prepared nanoparticles with obvious lower LCST and higher thermostability, but also obviously reduce the protein-repelling adsorption of films. Therefore, it is suggested to be used as protein-resistance coatings.

    7. Synthesis of water-soluble zwitterionic polysiloxanes

      Matthew Skinner, Ryan Selhorst and Todd Emrick

      Article first published online: 6 AUG 2015 | DOI: 10.1002/pola.27773

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      The facile preparation of water-soluble polysiloxanes containing pendent phosphorylcholine and sulfobetaine zwitterions is demonstrated. Zwitterionic polysiloxanes, synthesized by thiol-ene ‘click’ functionalization of vinyl-substituted siloxane polymers with zwitterionic thiols, were isolated with relatively high molecular weight and narrow molecular weight distribution. The surfactant characteristics and self-assembly behavior of these novel polymer amphiphiles in water are presented.

    8. Hyperbranched block copolymer from AB2 macromonomer: Synthesis and its reaction-induced microphase separation in epoxy thermosets

      Jingang Li, Yixin Xiang and Sixun Zheng

      Article first published online: 6 AUG 2015 | DOI: 10.1002/pola.27784

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      The synthesis of a hyperbranched block copolymer composed of poly(ε-caprolactone) (PCL) and polystyrene (PS) subchains via a copper-catalyzed Huisgen 1,3-dipolar cycloaddition polymerization is reported.

    9. Catalytic [2 + 2 + 2] cycloaddition polymerization of diyne–nitrile monomers in the presence of CoCl2-6H2O/diphosphine/Zn

      Yu-ki Sugiyama and Sentaro Okamoto

      Article first published online: 6 AUG 2015 | DOI: 10.1002/pola.27780

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      A cobalt-catalyzed [2 + 2 + 2] cocycloaddition reaction of 1,6-diynes and nitriles, providing substituted pyridines, has been applied to polymerization of diyne–nitrile monomers, the reaction of which proceeded smoothly in a step-growth fashion to provide linear polymers comprised with pyridine structure in a main chain.

    10. Copolymerization of isoprene with ethylene catalyzed by cationic half-sandwich fluorenyl scandium catalysts

      Gaixia Du, Jiaping Xue, Deqian Peng, Chao Yu, Hanghang Wang, Yuening Zhou, Jiaojiao Bi, Shaowen Zhang, Yuping Dong and Xiaofang Li

      Article first published online: 6 AUG 2015 | DOI: 10.1002/pola.27769

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      The cationic half-sandwich fluorenyl scandium species served as highly efficient and selective catalysts in isoprene polymerization and copolymerization with ethylene, affording cis−1,4-rich polyisoprenes and random or almost alternating isoprene-ethylene copolymers which are unavailable by the traditional catalysts. Besides, the isoprene incorporation and distribution in the copolymer chains can be controlled by changing the substituents of the fluorenyl ligand, thus generating different copolymers including 3,4-IP-alt-E and cis−1,4-IP-alt-E sequences.

    11. Synthesis and liquid crystalline behavior of bulky poly(methacrylamide)s

      Kylie B. Manning, Alexander G. Shtukenberg, Shane M. Nichols, Bart Kahr and Marcus Weck

      Article first published online: 6 AUG 2015 | DOI: 10.1002/pola.27774

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      RAFT polymerization of N-(bis(4-((2-ethylhexyl)oxy)phenyl)(phenyl)methyl)methacrylamide leads to soluble, helical polymers with lyotropic liquid crystalline properties at higher concentrations (10–15 wt %) in hexanes and chloroform.

    12. High solids TEMPO-mediated radical semibatch emulsion polymerization of styrene

      Roberto González-Blanco, Michael F. Cunningham and Enrique Saldívar-Guerra

      Article first published online: 6 AUG 2015 | DOI: 10.1002/pola.27771

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      A robust semicontinuous emulsion process for the nitroxide-mediated styrene polymerization is presented, using a bicomponent initiation system with TEMPO and potassium persulfate. Stable polystyrene latexes with solids contents of 5 to 40 wt %, high conversion (>95%), well controlled polymers (molecular weight dispersities lower than 1.4-1.5) and nitroxide efficiencies of nearly 100% are obtained, which constitutes a significant advance over prior efforts in TEMPO-mediated polymerization in aqueous dispersions.

  6. ArticleS

    1. Synthesis of high-order multiblock core cross-linked star polymers

      Thomas G. McKenzie, Jing M. Ren, Dave E. Dunstan, Edgar H. H. Wong and Greg G. Qiao

      Article first published online: 6 AUG 2015 | DOI: 10.1002/pola.27775

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      Core cross-linked star polymer nanoparticles with arms composed of sequence-defined multiblock copolymer structures have been synthesized for the first time via a one-pot copper-mediated controlled radical polymerization. The nature of the “arm-first” approach ensures that only linear macroinitiators with the desired block sequence are carried through to the final star structure. This technique represents a promising approach toward spatially resolved, sequence-defined polymeric nanoparticles.

  7. Articles

    1. Synthesis and characterization of polymer electrolytes based on cross-linked phenoxy-containing polyphosphazenes

      Chih-Hao Tsao, Mitsuru Ueda and Ping-Lin Kuo

      Article first published online: 6 AUG 2015 | DOI: 10.1002/pola.27781

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      A series of polymer electrolytes are prepared by reacting poly(phosphazene)s having 2-(2-methoxyethoxy)ethoxy and 2-(phenoxy)ethoxy units with 2,4,6-tris[bis(methoxymethyl)amino]-1,3,5-triazine (CYMEL) as a cross-linking agent. It is simple and reliable for controlling the cross-linking extent, thereby providing a straightforward way to produce a flexible polymer electrolyte membrane and useful model polymers to study the relationship between the cross-linking extents. The polymer electrolyte exhibits a maximum ionic conductivity of 5.36 × 10−5 S cm−1 at 100 °C.

    2. Synthesis of optically active conjugated polymers containing platinum in the main chain: Control of the higher-order structures by substituents and solvents

      Yu Miyagi, Takehiro Hirao, Takeharu Haino and Fumio Sanda

      Article first published online: 3 AUG 2015 | DOI: 10.1002/pola.27759

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      Novel optically active poly(phenyleneethynylene)s bearing platinum in the main chain were synthesized by the Sonogashira–Hagihara coupling polymerization of amino acid based optically active diiodoareylene monomers with a platinum-containing diethynyl monomer. Solvent effects on the higher-order structures were examined.

    3. PNVCL-PEGMA nanohydrogels with tailored transition temperature for controlled delivery of 5-fluorouracil

      Mirian A. González-Ayón, J. Adriana Sañudo-Barajas, Lorenzo A. Picos-Corrales and Angel Licea-Claverie

      Article first published online: 3 AUG 2015 | DOI: 10.1002/pola.27766

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      Preparation of N-vinylcaprolactam-based nano(hydro)gels without the use of emulsion stabilizers is demonstrated by means of surfactant free emulsion polymerization. Methacrylate functionalized polyethyleneglycol was used to provide the nanomaterials with a biocompatible, immune system “invisible,” shell. Two comonomers were incorporated to increase the transition temperature (Ttr): N-vinylpirrolidone (Ttr = 42 °C) and 2-methacryloyloxy benzoic acid (Ttr= 38 °C). The so tailored nano(hydro)gels showed faster release of the anticancer drug 5-fluorouracil at tumor conditions.

    4. Effect of side chain conjugation lengths on photovoltaic performance of two-dimensional conjugated copolymers that contain diketopyrrolopyrrole and thiophene with side chains

      You-Ren Liu, Li-Hsin Chan and Horng-Yi Tang

      Article first published online: 3 AUG 2015 | DOI: 10.1002/pola.27767

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      Two new 2D conjugated copolymers, called PDPPMTD and PDPPBTD, were designed and synthesized for use in PSCs. The findings herein suggest that the subtle tuning of the chemical structure of the side chains appeared significantly to influence the Jsc and FF.

    5. Azide-functionalized nanoparticles as quantized building block for the design of soft–soft fluorescent polystyrene core—PAMAM shell nanostructures

      Krystyna Baczko, Hélène Fensterbank, Bruno Berini, Nadège Bordage, Gilles Clavier, Rachel Méallet-Renault, Chantal Larpent and Emmanuel Allard

      Article first published online: 3 AUG 2015 | DOI: 10.1002/pola.27772

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      This work reports the covalent association of azido-coated nanoparticles, amino-terminated PAMAM dendrons, and a Bodipy derivative that leads to well-defined fluorescent dendrimer-based nanostructures in the 20–30 diameter range. These nano-objects display absorption and emission maxima above 500 nm with brightness the same order of magnitude as Qdots.

    6. Effect of limonene on the frontal ring opening metathesis polymerization of dicyclopentadiene

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

      Article first published online: 3 AUG 2015 | DOI: 10.1002/pola.27776

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      Frontal ring opening metathesis polymerization was successfully applied to the synthesis of copolymers of dicyclopentadiene and limonene. The presence of limonene was found to be crucial for many polymerization parameters and confers new and particular characteristics to polymer materials.

  8. Rapid Communication

    1. Dendritic hydrogels: From exploring various crosslinking chemistries to introducing functions and naturally abundant resources

      Surinthra Mongkhontreerat, Oliver C. J. Andrén, Assya Boujemaoui and Michael Malkoch

      Article first published online: 31 JUL 2015 | DOI: 10.1002/pola.27750

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      Dendritic hydrogels from dendritic-linear-dendritic (DLD) block copolymers based on PEG and bis-MPA dendrons were constructed via UV-initiated thiol-ene, thiol-yne, CuAAC, and amine-NHS crosslinking chemistries. Stoichiometric ratio manipulations, prior to film formation, resulted in functional hydrogels with tuneable compressive moduli. The highest gel fractions for all networks were obtained at off-stoichiometric ratios with surplus of DLDs. Finally, sustainable networks were fabricated by amalgamating DLD, naturally abundant cellulose nanocrystal, and protein-based bovine serum albumin.

  9. Articles

    1. A facile synthesis of catechol-functionalized poly(ethylene oxide) block and random copolymers

      Kaila M. Mattson, Allegra A. Latimer, Alaina J. McGrath, Nathaniel A. Lynd, Pontus Lundberg, Zachary M. Hudson and Craig J. Hawker

      Article first published online: 31 JUL 2015 | DOI: 10.1002/pola.27749

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      A modular strategy, starting from readily available methyl eugenol, to imbed protected catecholic moieties at controlled levels within polyethers is presented. This simple, high-yielding synthesis represents the first time catechols have been controllably dispersed throughout polyethylene oxide (PEO)-based polymer backbones. The precise tunability afforded by this system can enable systematic investigation of the effects that variables such as molecular weight, catechol incorporation, and catechol location can have on surface-anchored PEO.

    2. Photochemical stability of dicyano-substituted poly(phenylenevinylenes) with different side chains

      Logan P. Sanow, Jianyuan Sun and Cheng Zhang

      Article first published online: 31 JUL 2015 | DOI: 10.1002/pola.27755

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      The photodegradation mechanism study has been conducted on poly(2,5-dioctyl-1,4-phenylene-1,2-dicyanovinylene) (C8-diCN-PPV) and poly[2,5-bis(decyloxy)−1,4-phenylene-1,2-dicyanovinylene] (RO-diCN-PPV) to understand the reason behind the faster photodegradation of C8-diCN-PPV which has a lower LUMO. In both polymers, radical superoxide anion mechanism, which is responsible for electron-rich RO-PPVs, is found to be energetically unfavorable due to diCN substitution. Combined IR, UV–vis, photoluminescence, and phosphorescence spectroscopies study indicates that singlet oxygen is the main culprit for photodegradation of both polymers.

    3. A visible light responsive azobenzene-functionalized polymer: Synthesis, self-assembly, and photoresponsive properties

      Guojie Wang, Dong Yuan, Tingting Yuan, Jie Dong, Ning Feng and Guoxiang Han

      Article first published online: 29 JUL 2015 | DOI: 10.1002/pola.27747

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      An amphiphilic tetra-o-methoxy-substituted-azobenzene-functionalized poly(acrylic acid) was synthesized via the postpolymerization modification method, which can exhibit the trans-to-cis photoswitching under green light irradiation at 520 nm and the cis-to-trans photoswitching under blue light irradiation at 420 nm in both solution and aggregate state. The fluorescence of loaded Nile Red in the self-assembled polymer nanoparticles can be tuned upon the visible light irradiation.

    4. Graft modification of crystalline nanocellulose by Cu(0)-mediated SET living radical polymerization

      Hai-Dong Wang, Ryan D. Roeder, Ralph A. Whitney, Pascale Champagne and Michael F. Cunningham

      Article first published online: 28 JUL 2015 | DOI: 10.1002/pola.27754

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      Cu(0)-catalyzed SET living radical polymerization was used to graft poly(methyl acrylate) from a crystalline nanocellulose (CNC) surface. The polymer grafting step process exhibits fast polymerization kinetics and a very low level of copper consumption. The resulting polymerization medium is clear with almost no color, indicating low dissolved copper concentrations.

    5. Free radical polymerization of caffeine-containing methacrylate monomers

      Ashley M. Nelson, Sean T. Hemp, Jessica Chau and Timothy E. Long

      Article first published online: 28 JUL 2015 | DOI: 10.1002/pola.27756

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      A two-step synthesis involving a UV-induced photoreaction transformed the renewable resource caffeine into a polymerizable methacrylate. Free radical polymerization with 2-ethylhexyl methacrylate afforded novel copolymers containing covalently bound pendant caffeine. 1H NMR and UV-vis absorbance spectroscopy confirmed caffeine incorporation and SEC elucidated high molecular weight copolymers resulted. Caffeine increased both the glass transition temperature and modulus of the copolymers at low mol % incorporation revealing the potential for caffeine as a comonomer in thermoplastic elastomers.

    6. Synthesis of traditional and ionic polymethacrylates by anion catalyzed group transfer polymerization

      Veronika Strehmel and Volker Senkowski

      Article first published online: 28 JUL 2015 | DOI: 10.1002/pola.27760

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      Group transfer polymerization of ionic liquid methacrylates bearing the same anion as the hydrophobic ionic liquid used as solvent occurs more efficient compared to traditional methacrylates. The hydrophobic ionic liquid solvent influences group transfer polymerization of both traditional and ionic liquid methacrylates. The anion of the ionic liquid derives from a super acid. The ionic liquid additionally shows catalytic activity.

    7. Fabric-hydrogel composite membranes for culturing microalgae in semipermeable membrane-based photobioreactors

      Seung-Yong Lee, Z-Hun Kim, Hwa Yeon Oh, Younghoon Choi, Hanwool Park, Daewoo Jung, Jong-Min Kim, Yang Ho Na, Sang-Min Lim, Choul-Gyun Lee and Jin-Kyun Lee

      Article first published online: 28 JUL 2015 | DOI: 10.1002/pola.27770

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      Fabric-hydrogel composite membranes (FHCMs) are proposed as semipermeable materials for the construction of photobioreactors. A cotton fabric inside the hydrogel matrix endows the composite with tensile strength, which enables casting of FHCMs into thin membranes. In permeability coefficient measurements of inline image ions, it reached as high as 1.2 × 10−8 m2 min−1. In microalgal culture, a photobioreactor with a FHCM could maintain sufficient inline image ion concentration and pH of the culture broth, supporting microalgal growth.

    8. High refractive index materials: A structural property comparison of sulfide- and sulfoxide-containing polyamides

      Ali Javadi, Ebrahim Abouzari-Lotf, Shahram Mehdipour-Ataei, Masoumeh Zakeri, Mohamed Mahmoud Nasef, Arshad Ahmad and Adnan Ripin

      Article first published online: 28 JUL 2015 | DOI: 10.1002/pola.27764

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      Highly refractive polyamides bearing chlorine, sulfide, or sulfoxide linkages and ortho-linked patterned substitution are synthesized. Beside high solubility and thermal stability, the polymers exhibited desired optical properties including high optical transparency, high refractive indices, and low birefringence.

    9. PEGDA-based luminescent polymers prepared by frontal polymerization

      Javier Illescas, Yessica S. Ramírez-Fuentes, Gerardo Zaragoza-Galán, Pasquale Porcu, Alberto Mariani and Ernesto Rivera

      Article first published online: 28 JUL 2015 | DOI: 10.1002/pola.27768

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      Novel copolymers of PEGDA and 1-pyrenebutyl acrylate (PyBuAc), used as a fluorescent probe, were synthesized by radical polymerization. Besides, the optical properties of these materials were studied by absorption and fluorescence spectroscopy. The obtained copolymers exhibited a broad absorption band, and from the fluorescence spectra, no excimer emission was observed. It was possible to tune the color of the emitted light with the variation of the pyrene content in the samples.

    10. Synthesis and evaluation of new phosphonic acid-functionalized acrylamides with potential biomedical applications

      H. Betul Bingol, Ayse Altin, Tugba Bal, Sesil Agopcan-Cinar, Seda Kizilel and Duygu Avci

      Article first published online: 27 JUL 2015 | DOI: 10.1002/pola.27746

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      Three acrylamides containing phosphonic acid groups were synthesized and evaluated to investigate the relationship between monomer structure and polymerization reactivity/adhesion properties. They were found to be suitable for use as self-etching adhesive monomers because of their etching ability, hydrolytic stability, and copolymerizability with dental monomers. Furthermore, these monomers were used in the fabrication, characterization, and mineralization of hydrogels for tissue engineering applications.

    11. Light-induced controlled free radical polymerization of methacrylates using iron-based photocatalyst in visible light

      Ankushi Bansal, Pawan Kumar, Chandra D. Sharma, Siddharth S. Ray and Suman L. Jain

      Article first published online: 27 JUL 2015 | DOI: 10.1002/pola.27744

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      An efficient, inexpensive and less toxic iron-based photocatalyst is developed [i.e., Fe(bpy)3(PF6)2] for light-initiated controlled polymerization of methacrylates using α-bromoisobutyrate (EBriB) as an initiator under visible light.

    12. Biomimetic triblock and multiblock copolymers containing l-Phenylalanine moieties showing healing and enhanced mechanical properties

      Michael Hendrich, Lars Lewerdomski and Philipp Vana

      Article first published online: 27 JUL 2015 | DOI: 10.1002/pola.27753

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      Biomimetic triblock and multiblock copolymers of methyl acrylate and N-acryloyl-l-phenylalanine were synthesized via RAFT polymerization mimicking the structure of spider dragline silk. Tensile testing shows that the hydrogen bonding monomer induces a pronounced toughness increase. The new copolymers display a very strong healing effect, with the toughness being increased after drawing, breaking, and healing. Already, a very small content of only 0.1 mol % of N-acryloyl-l-phenylalanine improves the mechanical properties of these polymers significantly.

    13. Reactive copolymer functionalized graphene sheet for enhanced mechanical and thermal properties of epoxy composites

      Qiang Ma, Jing Luo, Yuanxun Chen, Wei Wei, Ren Liu and Xiaoya Liu

      Article first published online: 24 JUL 2015 | DOI: 10.1002/pola.27751

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      A novel reactive copolymer VCz–GMA containing carbazole and epoxide group was designed, synthesized and employed to noncovalently functionalize graphene sheet (GNS) for preparing epoxy nanocomposites with enhanced mechanical properties. VCz–GMA facilitates the exfoliation/dispersion level of GNs in epoxy matrix and serves as a linker between GNS and epoxy with improved compatibility and interfacial interaction. The obtained composite showed a remarkable enhancement in both mechanical and thermal property than either the pure epoxy or the GNS/epoxy composites.

  10. Rapid Communication

    1. You have free access to this content
      New approach for producing fluorescent gold nanoparticles: Poly(ethylene oxide) homopolymers as reductants in the micelles of amphiphilic fluorosilicone-containing block copolymers

      Jiawen Zhang, Lingmin Yi, Kai Xu, Jing Li and Dongzhi Lai

      Article first published online: 24 JUL 2015 | DOI: 10.1002/pola.27758

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      The reduction of gold salts by poly(ethylene oxide) (PEO) homopolymer is very slow and more than 2 days is needed to produce gold nanoparticles (AuNPs). In this work, however, AuNPs are rapidly produced in the micelles of novel amphiphilic poly[methyl(3,3,3-trifluoropropyl)siloxane]-b-poly(acrylic acid) (PMTFPS-b-PAA) block copolymers when using PEO as the reductant. Moreover, fluorescent AuNPs in the block copolymer micelles are presented by a direct monitoring of the micelle shape and the solution optical properties..

    2. You have free access to this content
      Controlled synthesis of hyperbranched polythioether polyols and their use for the fabrication of porous anatase nanospheres

      Xinhua Huang, Trinh Thi Kim Hoang, Hye Ri Lee, Huiju Park, Jin Ku Cho, Yongjin Kim and Il Kim

      Article first published online: 24 JUL 2015 | DOI: 10.1002/pola.27761

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      A series of new hyperbranched polymers bearing multiple ether, thioether, and hydroxyl groups are synthesized by the oxyanionic ring-opening multi-branching polymerization of the AB3 type monomer prepared by the click reaction of 4-vinyl-cyclohexene-1,2-epoxide with 1-thiolglycerol. The resulting HBPs are proven to be good “molds” to control the nucleation and growth of titanium-oxo-species during a sol–gel mineralization process, yielding discrete porous anatase nanospheres (30–100 nm).

  11. Articles

    1. Nanopatterning and micropatterning of cobalt containing block copolymers via phase-separation and lithographic techniques

      Mahboubeh Hadadpour and Paul J. Ragogna

      Article first published online: 17 JUL 2015 | DOI: 10.1002/pola.27745

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      Solution self-assembly of a BCP consisting of cobalt containing metallopolymer block and a PDMS block resulted in spherical micelles with metallic core and PDMS corona. Solid-state self-assembly produces hexagonal domains of metallopolymer in a PDMS matrix. Magnetic ceramic is produced by pyrolysis of the bulk self-assembled BCP. This material is used as ink in pattern transfer via the μCP lithography method.

    2. Versatile and controlled functionalization of polyferrocenylsilane-b-polyvinylsiloxane block copolymers using a N-hydroxysuccinimidyl ester strategy

      Charlotte E. Boott, David J. Lunn and Ian Manners

      Article first published online: 14 JUL 2015 | DOI: 10.1002/pola.27727

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      This article reports the introduction of a N-hydroxysuccinimidyl ester group onto the pendant vinyl group of poly(ferrocenyldimethyl)silane-b-polyvinylsiloxane copolymers which provides a route to incorporate a range of functionalities previously inaccessible using other methods.

    3. Low-potential facile electrosynthesis of free-standing poly(1H-benzo[g]indole) film as a yellow-light-emitter

      Ling Wang, Dan Zhao, Changlong Liu and Guangming Nie

      Article first published online: 7 JUL 2015 | DOI: 10.1002/pola.27738

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      Free-standing poly(1H-benzo[g]indole) films are synthesized electrochemically in boron trifluoride diethyl etherate at low potentials. Poly(1H-benzo[g]indole) with low band gap value (1.59 eV) shows good electrochemical behavior and better thermal stability. Fluorescent spectral studies indicate that solid-state Poly(1H-benzo[g]indole) film is a good yellow-light-emitter.

  12. Rapid Communication

    1. You have free access to this content
      Preparation of base-amplifying microcapsules and their application to photoreactive materials

      Koji Arimitsu, Yune Kumazawa and Masahiro Furutani

      Article first published online: 7 JUL 2015 | DOI: 10.1002/pola.27737

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      Base-amplifying (BA) microcapsules are developed, and it is found that they work more effectively than dispersed molecular base amplifiers in anionic UV curing systems with a water-soluble epoxy resin. The pencil-hardness value of 2H is obtained with the BA microcapsules after 5000 mJ cm−2 of 365 nm light irradiation and subsequent heating at 100 °C for 60 min.

  13. Articles

    1. Cyclopentyl methyl ether: A new green co-solvent for supplemental activator and reducing agent atom transfer radical polymerization

      Pedro Maximiano, Joana P. Mendes, Patrícia V. Mendonça, Carlos M. R. Abreu, Tamaz Guliashvili, Arménio C. Serra and Jorge F. J. Coelho

      Article first published online: 4 JUL 2015 | DOI: 10.1002/pola.27736

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      A new green solvent, cyclopentyl methyl ether, is used for the first time in solvent mixtures for the successful supplemental activator and reducing agent atom transfer radical polymerization of both activated and non-activated monomers. The “green” nature of the solvent along with the use of low concentrations of soluble metal catalyst during the polymerization makes this technique very attractive for the preparation of polymers for biomedical applications.

    2. RAFT made methacrylate copolymers for reversible pH-responsive nanoparticles

      Turgay Yildirim, Alexandra C. Rinkenauer, Christine Weber, Anja Traeger, Stephanie Schubert and Ulrich S. Schubert

      Article first published online: 2 JUL 2015 | DOI: 10.1002/pola.27734

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      A library of well-defined copolymers of methyl methacrylate (MMA) with 2-(dimethylamino) ethyl methacrylate (DMAEMA), 2-(tert-butylamino)ethylmethacrylate (tBAEMA) and 2-aminoethyl methacrylate hydrochloride (AEMA HCI) was synthesized via RAFT polymerization. The controlled nature of the radical polymerization was demonstrated by kinetic studies. Well-defined nanoparticles from the synthesized copolymers with varying sizes were successfully prepared via the nanoprecipitation method. Depending on the structure and amount of the amino content, the obtained nanoparticles reveal a reversible pH-response. The nanoparticles did not exhibit any cytotoxic effect on L929 cells.

    3. Biocompatible amphiphilic conetwork based on crosslinked star copolymers: A potential drug carrier

      Haiye Wang, Aiwen Qin, Xiang Li, Xinzhen Zhao, Dapeng Liu and Chunju He

      Article first published online: 30 JUN 2015 | DOI: 10.1002/pola.27721

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      Novel “core-first” star polymer-based conetworks were successfully fabricated via sequential atom transfer polymerization. The amphiphilic conetworks (APCNs) exhibit unique swelling behavior, excellent mechanical properties, distinct phase separation, and good cytocompatibility, which are suitable for sustained controlled release of choline theophyllinate where the release rate can be regulated by varying the hydrophilic (HI) composition and crosslinking density. The overall results suggest that APCN is a promising candidate as a drug carrier.

    4. Synthesis of new optically active α,α′,β-trisubstituted-β-lactones as monomers for stereoregular biopolyesters

      Rima Belibel and Christel Barbaud

      Article first published online: 30 JUN 2015 | DOI: 10.1002/pola.27724

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      The use of biodegradable and bioassimilable stereopolymers is innovative for temporary therapeutic applications. Stereopolyesters derived from malic acid were synthesized by anionic polymerization from new optically active α,α′,β-trisubstituted-β-lactones as monomers. The total synthesis and characterization of a series of design lactones and one isotactic homopolyester are described in detail.

    5. Random propene/4-methyl-1-pentene copolymers synthesized with C2 symmetric highly isospecific metallocenes

      Maria Carmela Sacchi, Simona Losio, Luigi Fantauzzi, Paola Stagnaro, Roberto Utzeri and Maurizio Galimberti

      Article first published online: 30 JUN 2015 | DOI: 10.1002/pola.27725

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      Random propene-based copolymers with a 1-olefin such as 4-methyl-1-pentene (Y), within a wide range of compositions, are prepared with the highly isospecific single site catalyst, rac-CH2(3- t BuInd)2ZrCl2. This finding is against what is acknowledged in the field and provides a novel strategy for the preparation on a large scale of random propene-based copolymers by properly selecting the metallocene/comonomer combination.

    6. Thermoresponsive polymersome from a double hydrophilic block copolymer

      Prithankar Pramanik and Suhrit Ghosh

      Article first published online: 29 JUN 2015 | DOI: 10.1002/pola.27735

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      Neither micelle nor gel, well-defined nano vesicles were prepared by thermally triggered self-assembly of a PEO-b-PNIPAm copolymer having an appropriate hydrophobic/hydrophilic balance.

  14. Original Articles

    1. Synthesis of poly(2-oxazoline)s with side chain methyl ester functionalities: Detailed understanding of living copolymerization behavior of methyl ester containing monomers with 2-alkyl-2-oxazolines

      Petra J. M. Bouten, Dietmar Hertsen, Maarten Vergaelen, Bryn D. Monnery, Saron Catak, Jan C. M. van Hest, Veronique Van Speybroeck and Richard Hoogenboom

      Article first published online: 29 JUN 2015 | DOI: 10.1002/pola.27733

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      Poly(2-oxazoline)s can be prepared by cationic ring opening polymerization. Kinetic studies of the homo- and copolymerization of methyl ester containing 2-oxazoline monomers were performed showing a faster propagation for the methyl ester containing monomers than for alkyl monomers. Surprisingly in copolymerization these rates are inversed, yielding gradient copolymers. These observations are supported by computational studies, confirming that methyl ester groups increase nucleophilicity of the living chain end.

  15. Articles

    1. Influence of functionality on direct arylation of model systems as a route toward fluorinated copolymers via direct arylation polymerization (DArP)

      Francesco Livi, Nemal S. Gobalasingham, Eva Bundgaard and Barry C. Thompson

      Article first published online: 29 JUN 2015 | DOI: 10.1002/pola.27728

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      The synthesis of a defect-free fluorinated copolymer through direct arylation polymerization of a thiophene-containing monomer and a highly fluorinated benzene monomer is reported. A small molecule direct arylation screening on similar substrates is carried out in order to obtain the best conditions for the polymerizations reaction. The functionalization of the monomers has a strong influence on the product outcome, both in case of small molecules and copolymers.

    2. Enhanced spin capturing polymerization: Numerical investigation of mechanism

      Sergey V. Nikitin, Dmitriy A. Parkhomenko, Mariya V. Edeleva and Elena G. Bagryanskaya

      Article first published online: 25 JUN 2015 | DOI: 10.1002/pola.27723

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      Simulations of kinetics of enhanced spin capturing polymerization were performed to reveal key factors that affect the parameters of the polymer obtained by this technique. Criteria for success were formulated allowing for an estimation of polymerization behavior prior to the experiment.

    3. A facile method to synthesize high-molecular-weight biobased polyesters from 2,5-furandicarboxylic acid and long-chain diols

      Vasilios Tsanaktsis, George Z. Papageorgiou and Dimitrios N. Bikiaris

      Article first published online: 25 JUN 2015 | DOI: 10.1002/pola.27730

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      Biobased 2,5-furandicarboxylate polyesters with long-chain diols are synthesized successfully using the dimethylester of 2,5-dicarboxylic acid and diols containing 8–12 methylene groups. Because of the high boiling point of these diols and their high distillation difficulty, a new method was proposed to produce polyesters with high molecular weight. All polyesters are semicrystalline materials with appropriate mechanical properties, which depend on the methylene group number.

    4. Substituent effect of N-aryl-N′-pyridyl ureas as thermal latent initiators on ring-opening polymerization of epoxide

      Naoyuki Makiuchi, Atsushi Sudo and Takeshi Endo

      Article first published online: 25 JUN 2015 | DOI: 10.1002/pola.27726

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      A series of N-aryl-N′-pyridyl ureas having various substituent on the aryl moiety were synthesized and studied as thermally latent initiators for the ring-opening polymerization of epoxides. DSC measurement for formulations comprised of DGEBA and the ureas clarified that relationship between the reaction temperature and the electron density of the aromatic ring of the ureas.

    5. Thermo- and pH-sensitive triblock copolymers with tunable hydrophilic/hydrophobic properties

      Christophe Pottier, Gaëlle Morandi, Virginie Dulong, Zied Souguir, Luc Picton and Didier Le Cerf

      Article first published online: 25 JUN 2015 | DOI: 10.1002/pola.27729

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      Synthesis and characterization of multiresponsive P(AA-co-tBA)-b-PPO-b-P(AA-co-tBA) triblock copolymers are presented. These copolymers were elaborated by atom transfer radical polymerization (ATRP) and partial hydrolysis of tert-butyl acrylate (tBA) moieties providing both control on the outer blocks length and on the acrylic acid (AA)/tBA composition. The self-assembly of the triblock copolymers in aqueous solution is demonstrated to be dependent on the hydrophilic/lipophilic composition. Moreover, copolymers show thermo- and pH-sensitive properties due to deshydratation of poly(propylene oxide) (PPO) block and ionization of PAA blocks.

    6. Control through monomer placement of surface properties and morphology of fluoromethacrylate copolymers

      Ao Chen, Idriss Blakey, Kevin S. Jack, Andrew K. Whittaker and Hui Peng

      Article first published online: 25 JUN 2015 | DOI: 10.1002/pola.27731

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      The effect of polymer placement on surface energy and bulk morphology was investigated for block and statistical copolymers of methyl methacrylate and 2,2,3,3,4,4,4-heptafluorobutyl methacrylate (F3MA). Incorporation of the fluoromonomer lowered the surface energy, and the decrease was more significant for the polymer with block structure. The bulk phase structure for the block copolymers ranged from cylindrical to spherical depending on the copolymer composition. A value of the solubility parameter for polymers of F3MA was determined.

    7. Synthesis of polyphosphodiesters by ring-opening polymerization of cyclic phosphates bearing allyl phosphoester protecting groups

      Benoït Clément, Daniel G. Molin, Christine Jérôme and Philippe Lecomte

      Article first published online: 25 JUN 2015 | DOI: 10.1002/pola.27732

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      Anionic aliphatic polyphosphodiesters are synthesized by a new strategy based on the ring-opening polymerization of a cyclic phosphate bearing an allyl phosphoester protecting group. The deprotection is achieved by reaction with sodium benzenethiolate in the absence of any detectable degradation. No transition metal is involved at any step of the process (the synthesis of the monomer, the polymerization and the final deprotection).

    8. You have free access to this content
      Synthesis, Characterization, and thermoresponsive properties of Helical Polypeptides Derivatized from Poly(γ−4-(3-chloropropoxycarbonyl)benzyl-L-glutamate)

      Yong Deng, Xi Wang, Qiulin Yuan, Mengxiang Zhu, Ying Ling and Haoyu Tang

      Article first published online: 23 JUN 2015 | DOI: 10.1002/pola.27708

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      Two types of helical polypeptides bearing oligo-ethylene-glycol (OEG) groups or 1-butylimidazolium salts have been prepared from poly−4-(3-chloropropoxy-carbonyl)benzyl-L-glutamate) with high grafting densities. Polymers bearing 1-butylimidazolium and I counter-anions exhibited reversible UCST-type transitions in water. Polymers bearing OEG3 side-chains showed reversible LCST-type phase transition behaviors in water and reversible UCST-type phase transition behaviors in various organic solvents.

    9. The effect of molecular weight on the separation of semiconducting single-walled carbon nanotubes using poly(2,7-carbazole)s

      Nicole A. Rice, Ayyagari V. Subrahmanyam, Scott E. Laengert and Alex Adronov

      Article first published online: 19 JUN 2015 | DOI: 10.1002/pola.27715

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      The molecular weight of poly(2,7-carbazole)s has an impact on their ability to selectively disperse semiconducting single-walled carbon nanotubes (SWNTs) in THF. Molecular weights below 30 kDa result in dispersions containing mixtures of semiconducting and metallic structures, while above 30 kDa, a high degree of selectivity for semiconducting SWNTs is observed.

  16. Rapid Communication

    1. You have free access to this content
      Combined atom-transfer radical polymerization and ring-opening polymerization to design polymer–polypeptide copolymer conjugates toward self-aggregated hybrid micro/nanospheres for dye encapsulation

      Anupam Saha, Tapas K. Paira, Mrinmoy Biswas, Somdeb Jana, Sanjib Banerjee and Tarun K. Mandal

      Article first published online: 17 JUN 2015 | DOI: 10.1002/pola.27713

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      A designed orthogonal dual initiator is employed to construct poly(methyl methacrylate)-block-polytyrosine copolymer conjugates via the combination of atom-transfer radical polymerization of methyl methacrylate, “click” chemistry and ring-opening polymerization of tyrosine–α-amino acid N-carboxyanhydride monomer. The polymer–polypeptide conjugate undergoes self-aggregation in dimethylformamide to produce hybrid micro/nanospheres owing to the formation of composite micelle as evidenced from field emission scanning electron microscopy and dynamic light scattering study. A simple solution-based approach is described to encapsulate an organic dye (Rhodamine-6G) into the aggregated hybrid micro/nanospheres.

  17. Articles

    1. Utilization of poly(vinylchloride) and poly(vinylidenefluoride) as macroinitiators for ATRP polymerization of hydroxyethyl methacrylate: Electroanalytical and graft-copolymerization studies

      Sonia Lanzalaco, Alessandro Galia, Flavia Lazzano, Rosalia Rita Mauro and Onofrio Scialdone

      Article first published online: 17 JUN 2015 | DOI: 10.1002/pola.27717

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      The utilization of poly(vinylchloride) and poly(vinylidenefluoride) as macroinitiators for atom transfer radical polymerization of hydroxyethyl methacrylate was studied. Electroanalytical investigations and “grafting from” experiments suggest that both C[BOND]Cl and C[BOND]F bonds can be cleaved by Cu based catalytic systems to generate macroradicals. Lower grafting levels were obtained in the case of the fluorinated polymer probably as a consequence of the higher strength of the C[BOND]F bond.

    2. Poly[N-(10-oxo-2-vinylanthracen-9(10H)-ylidene)cyanamide] as a novel cathode material for li-organic batteries

      Daniel Schmidt, Bernhard Häupler, Christian Stolze, Martin D. Hager and Ulrich S. Schubert

      Article first published online: 17 JUN 2015 | DOI: 10.1002/pola.27716

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      Poly[N-(10-oxo-2-vinylanthracen-9(10H)-ylidene)cyanamide] as a novel cathode material for Li-organic batteries The application of polymers bearing N-(10-oxo-anthracen-9(10H)-ylidene)cyanamide units as electrode material in lithium organic batteries enables a charge/discharge device featuring a cell potential of 2.3 V, a theoretical capacity of 207 mAh/g and a good stability (100 cycles, 15% loss).

    3. Versatile soluble oligomeric styrene supports for peptide synthesis

      Venkataramana Erapalapati and Nandita Madhavan

      Article first published online: 17 JUN 2015 | DOI: 10.1002/pola.27714

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      Soluble styrene oligomers incorporated with high loading capacities are used to load a variety of amino acids in 59–85% yields. The supports are used to synthesize hexapeptides in 50% yields using only 2 equivalents of coupling reagents. The support synthesis is modular enabling incorporation of any styrene derived attachment site onto the highly soluble oligomer backbone.

    4. Radical Polymerization of methacrylates with an adamantane-like rigid core derived from naturally occurring myo-inositol

      Shusuke Okamoto, Shohei Onoue, Mami Muramatsu, Shimpei Yoshikawa and Atsushi Sudo

      Article first published online: 16 JUN 2015 | DOI: 10.1002/pola.27705

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      myo-Inositol orthoester was converted into tri- and dimethacrylate monomers with a rigid adamantane-like core. The radical polymerization of trimethacrylate and its copolymerization with methyl methacrylate yielded networked polymers that exhibited higher thermal stability than those of networked polymers with a less rigid cyclohexane structure at the crosslinking points. Analyzing the radical polymerization of dimethacrylate provided an insight into the polymer structure. The process advanced in a cyclopolymerization manner to yield polymers with high glass transition temperature of up to 285°C through the incorporation of rigid cyclic structures into the repeating unit.

    5. Oxime functionalization strategy for iodinated poly(epsilon-caprolactone) X-ray opaque materials

      Samantha E. Nicolau, Lundy L. Davis, Caroline C. Duncan, Timothy R. Olsen, Frank Alexis, Daniel C. Whitehead and Brooke A. Van Horn

      Article first published online: 16 JUN 2015 | DOI: 10.1002/pola.27706

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      A novel "Click" postpolymerization strategy for the preparation of x-ray opaque polycaprolactone is presented. The final functional copolymer products were achieved by (1) a random copolymerization with a functional caprolactone comonomer, (2) deprotection of the comonomer repeat units, and (3) the acid-catalyzed oxime postpolymerization ligation of a hydroxylamine bearing iodine. Rigorous structural and thermal characterization were performed to confirm the identity and functionality of the radio-opaque materials.

    6. The effect of amide solvent structure on the direct arylation polymerization (DArP) of 2-Bromo-3-hexylthiophene

      Andrey E. Rudenko and Barry C. Thompson

      Article first published online: 16 JUN 2015 | DOI: 10.1002/pola.27712

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      The effect of amide solvent structure on the properties of DArP P3HT is explored. The results indicate that the amide structure must be acyclic and contain alkyl substituents of sufficient, but not excessive steric bulk to promote efficient polymerization. The resulting polymers contain a minimal content of structural defects and possess attractive physical properties.

    7. Degradable poly(ester triazole)s based on renewable resources

      Khalid Hakkou, Manuel Bueno-Martínez, Inmaculada Molina-Pinilla and Juan A. Galbis

      Article first published online: 16 JUN 2015 | DOI: 10.1002/pola.27710

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      Novel degradable linear polymers have been prepared from carbohydrates such as glucose, arabinose, and erythrose by copper(I)-catalyzed alkyne-azide cycloaddition click polymerization. These polymers contain in their repeating units two or more free secondary alcohol functions which were used to prepare some network structures by crosslinking reaction with hexamethylene diisocyanate.

    8. Synthesis and radical polymerization of methacrylate endowed with bicyclobis(γ-butyrolactone) moiety through methylene linker

      Ryu Yamasaki, Atsushi Sudo and Takeshi Endo

      Article first published online: 12 JUN 2015 | DOI: 10.1002/pola.27707

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      A series of novel methacrylates bearing a highly polar and rigid bicyclobis(γ-butyrolactone) (BBL) moiety were synthesized and radically polymerized to afford the corresponding poly(methacrylate)s. The incorporation of BBL structure in the side chain endowed the polymers with good solubility in aprotic polar solvents and high glass transition temperatures up to 138 °C.

    9. Postfunctionalization of polyoxanorbornene backbone through the combination of bromination and nitroxide radical coupling reactions

      Lale Nur Atici, Erhan Demirel, Umit Tunca, Gurkan Hizal and Hakan Durmaz

      Article first published online: 4 JUN 2015 | DOI: 10.1002/pola.27697

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      A well-defined poly(oxanorbornene imide) (PONB) was prepared and reacted with bromine yielding PONB-Br which was further reacted with acrylate, epoxy and poly(ethylene glycol) (PEG) functionalized 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) under Cu(0)/CuBr/PMDETA catalyst condition in N,N-dimethylformamide (DMF) at room temperature overnight affording PONB-acrylate, PONB-epoxy and PONB-PEG through the nitroxide radical coupling (NRC) reaction.

    10. Synthesis and crosslinking of hyperbranched poly(n-nonyl acrylate) to form organogels

      Yangtian Lu, Dibyendu Debnath, R. A. Weiss and Coleen Pugh

      Article first published online: 3 JUN 2015 | DOI: 10.1002/pola.27700

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      (2-Bromo-n-nonan-1-oxycarbonyl)ethyl acrylate was homopolymerized and copolymerized by atom transfer radical polymerization (ATRP) and activator generated by electron transfer (AGET) ATRP to produce soluble polymers. The resulting hyperbranched (co)polymers undergo very efficient radical–radical crosslinking reaction by atom transfer radical coupling, resulting in hard plastic particles from the homopolymer of (2-bromo-n-nonan-1-oxycarbonyl)ethyl acrylate synthesized in bulk. Crosslinked organogels that swell in THF were formed when the rate of crosslinking decreased using acetonitrile solutions.

    11. Soft Matter Nanoparticles with Reactive Coronal Pentafluorophenyl Methacrylate Residues via Non-Polar RAFT Dispersion Polymerization and Polymerization-Induced Self-Assembly

      Yiwen Pei, Janina-Miriam Noy, Peter J. Roth and Andrew B. Lowe

      Article first published online: 2 JUN 2015 | DOI: 10.1002/pola.27696

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      The concept of non-polar polymerization-induced self-assembly has been used for the synthesis of soft matter nanoparticles with spherical, worm, and vesicular morphologies containing reactive pentafluorophenyl methacrylate (PFPMA) in the nano-object coronae. The reaction of the PFPMA repeat units of the nanoparticles with small molecule primary amines yielded a new family of nanoparticles containing interesting surface-bound functionality.

    12. A New D–A conjugated polymer P(PTQD-BDT) with PTQD acceptor and BDT donor units for BHJ polymer solar cells application

      M. L. Keshtov, S. A. Kuklin, F. C. Chen, A. R. Khokhlov, Rajnish Kurchania and G. D. Sharma

      Article first published online: 29 MAY 2015 | DOI: 10.1002/pola.27699

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      A donor–acceptor copolymer P(PTQD0BDT) comprising of weak a BDT unit and strong PTQD unit was synthesized and used as a donor for the fabrication of bulk heterojunction (BHJ) polymer solar cells. The BHJ solar cell with optimized P(PTQD-BDT): PC71BM (1:2) active layer processed with 3% v DIO/CF showed power conversion efficiency of 5.55%.

    13. Reduction-cleavable hyperbranched polymers with limited intramolecular cyclization via click chemistry

      Heng Chen, Jiqiong Jia, Xiao Duan, Zhen Yang and Jie Kong

      Article first published online: 28 MAY 2015 | DOI: 10.1002/pola.27694

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      Reduction-cleavable hyperbranched polymers with limited intramolecular cyclization were achieved via click chemistry. The rigid triazole units generated from CuAAC click chemistry limited and reduced the intramolecular cyclization as well as the disulfide bonds introduced by A2 monomer gave the reduction-cleavable feature of the resulting hyperbranched polymers. The reduction-cleavable hyperbranched poly(ester triazole)s with limited intramolecular cyclization are expected to possess potential in the application of stimuli-responsive anticancer drug nanocarriers.

    14. Norbornene derivatives from a metal-free, strain-promoted cycloaddition reaction: New building blocks for ring-opening metathesis polymerization reactions

      Christopher E. Hobbs, Binhong Lin and Thomas Malinski

      Article first published online: 21 MAY 2015 | DOI: 10.1002/pola.27691

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      A facile 1,3-dipolar cycloaddition between azides and norbornadiene is used for the preparation of new monomers for ring-opening metathesis polymerization (ROMP) reactions. These species can be obtained under solvent-and catalyst-free reaction conditions and copolymerized with other norbornenes to provide new, functionalized polymers. Further polymer functionalization can be obtained through a thermal loss of N2.

    15. Synthesis and characterization of benzimidazolium-functionalized polysulfones as anion-exchange membranes

      María Teresa Pérez-Prior, Alejandro Várez and Belén Levenfeld

      Article first published online: 21 MAY 2015 | DOI: 10.1002/pola.27692

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      A series of benzimidazolium-functionalized polysulfones were synthesized and characterized. The electrochemical behavior of the resulting anion-exchange membranes showed a clear dependence with the degree of chloromethylation of polysulfone. Thus, the ionic conductivity increased more than two orders of magnitude when the degree of chloromethylation increased from 40 to 140%. In addition, the presence of benzimidazolium groups instead of the widely used quaternary ammonium ones improved the ionic conductivity of the polymeric membranes.

    16. Synthesis of hyperbranched polyacetals via an + b2-type polyaddition (n = 3, 8, 18, and 21): Candidate resists for extreme ultraviolet lithography

      Hiroto Kudo, Shuhei Matsubara, Hiroki Yamamoto and Takahiro Kozawa

      Article first published online: 19 MAY 2015 | DOI: 10.1002/pola.27686

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      Hyperbranched polyacetals were synthesized by means of An + B2-type polyaddition reaction (n = 3, 8, 18, and 21). The physical properties, including solubility, thermal stability, and film-forming ability, and the photo-induced degradation reactivity under ultraviolet (UV) exposure and solubility-switch using an extreme UV exposure tool were consistent with potential applicability of poly(THPE-co-BVOC) and poly(CRA[4]-co-BVOC) as next-generation photo-resist materials.

    17. RAFT polymerization in supercritical carbon dioxide based on an induced precipitation approach: Synthesis of 2-ethoxyethyl methacrylate/acrylamide block copolymers

      Gerard Hawkins, Per B. Zetterlund and Fawaz Aldabbagh

      Article first published online: 13 MAY 2015 | DOI: 10.1002/pola.27688

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      A new controlled/living heterogeneous polymerization technique in benign supercritical CO2 is described involving the formation of monomer-swollen seed particles by precipitation of MacroRAFT agent prior to polymerization. The technique offers the large scale synthesis of poly(2-ethoxyethyl methacrylate)-b-poly(acrylamides) useful for biomedical applications, which can be isolated as powders at high conversion circumventing the requirement for volatile organic solvents.

    18. Preparation of microporous polymers in the form of particles and a thin film from hyperbranched polyphenylenes

      Min Chul Cha, Yoonbin Lim and Ji Young Chang

      Article first published online: 29 APR 2015 | DOI: 10.1002/pola.27670

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      A hyperbranched polyphenylene with numerous unreacted bromophenyl end groups was used as a multifunctional building block for the synthesis of a microporous organic polymer. The precursor polymer could be shaped into a film and the subsequent cross-linking reaction produced an insoluble porous film.

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