Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 53 Issue 9

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

Impact Factor: 3.245

ISI Journal Citation Reports © Ranking: 2013: 14/82 (Polymer Science)

Online ISSN: 1099-0518

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

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  1. 1 - 66
  1. Articles

    1. Synthesis, characterization, and photovoltaic properties of dithienylbenzobisazole-dithienylsilole copolymers

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

      Article first published online: 28 MAR 2015 | DOI: 10.1002/pola.27603

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      Three donor-acceptor copolymers based on a donor-acceptor-donor triad of either cis-benzbisoxazole, trans-benzobisoxazole or trans-benzobisthiazole and dioctyl-dithieno-[2,3-b:2',3'-d]silole were synthesized. The impact of these structural modifications on the optical, electrochemical, and morphological properties of the polymers were investigated. The performance of these copolymers in photovoltaic cells is also reported.

    2. Synthesis of dual-functional poly(6-azidohexylmethacrylate) brushes by a RAFT agent carrying carboxylic acid end groups

      Dilek Cimen, Ertan Yildirim and Tuncer Caykara

      Article first published online: 28 MAR 2015 | DOI: 10.1002/pola.27613

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      A novel dual-functional surface-attached polymer brush was synthesized by an interface-mediated RAFT polymerization. This interface-mediated RAFT polymerization produced silicon substrate coated with dual-functional (azido groups from monomer and carboxylic acid groups from RAFT agent) poly(6-azidohexylmethacrylate) [poly(AHMA)] brush with a grafting density as high as 0.59 chains/nm2. The azido groups of the poly(AHMA) brushes can be modified with alkyl groups via “CuAAC” click reaction, while the carboxylic acid end groups can be reacted with amine groups via amide reaction.

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      Synthesis of polyacrylonitrile mediated by manganese(III) acetylacetonate (Mn(acac)3) and 2-cyanoprop-2-yl dithionaphthalenoate

      Yuanyuan Xu, Jinming Sun, Hou Chen, Liangjiu Bai, Qian Tao, Lili Yu and Yating Wang

      Article first published online: 28 MAR 2015 | DOI: 10.1002/pola.27600

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      PAN was successfully synthesized with Mn(acac)3 as the initiator, and CPDN as the CTA. The novel polymerization complied with a typical RAFT polymerization mechanism. The initial radicals was produced via pyrolysis of Mn(acac)3. Compared with that initiated by AIBN, the polymerization showed better "living"/controlled features with Mn(acac)3 as the initiator.

  3. Articles

    1. Functional dye as a comonomer in a water-soluble polymer

      Wenwen Zhang, Nelson R. Vinueza, Preeta Datta and Stephen Michielsen

      Article first published online: 28 MAR 2015 | DOI: 10.1002/pola.27592

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      An antimicrobial dye Rose Bengal has been incorporated into a water-soluble copolymer to achieve effective and durable properties. The final product has been characterized from aspects of the percentage of free dye percentage, solubility, and singlet oxygen production rate, which indicates an effective approach to make low cost, sustainable, and durable antimicrobial products by applying this polymer solution to various surfaces.

    2. Synthesis and copolymerization of oligo(lactic acid) derived norbornene macromonomers with amino acid derived norbornene monomer: Formation of the 3D macroporous scaffold

      Sutthira Sutthasupa, Fumio Sanda, Kajornsak Faungnawakij and Puttinan Meepowpan

      Article first published online: 28 MAR 2015 | DOI: 10.1002/pola.27604

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      Ring-opening metathesis copolymerizations of amino acid and (oligo)lactic acid-derived novel norbornene monomers using the Grubbs 2nd generation catalyst proceeded satisfactorily. The 3D porous polymer samples were obtained by drying of the polymers under reduced pressure. The average pore sizes of the copolymers increased as the ratios of (oligo)lactic acid unit increased. The copolymers showed higher mechanical strength than the homopolymers, presumably due to enhancement of the intermolecular hydrogen bonding between the amide groups and/or the hydroxy/ester groups.

    3. Rubbery wound closure adhesives. I. design, synthesis, characterization, and testing of polyisobutylene-based cyanoacrylate homo- and co-networks

      Istvan Szanka, Amalia Szanka, Sinan Şen, Nihan Nugay and Joseph P. Kennedy

      Article first published online: 28 MAR 2015 | DOI: 10.1002/pola.27606

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      Novel rubbery wound closures containing various proportions and molecular weights of polyisobutylene (PIB) and poly(2-octyl cyanoacrylate) [P(OctCA)] for potential clinical use were designed, synthesized, characterized, and tested. Co-networks were prepared by copolymerizing Ø(PIB-CA)3 with OctCA using N-dimethyl-p-toluidine (DMT). Strips of porcine skin coated with select co-networks could be repeatedly stretched, flexed, and twisted without compromising the integrity of the membrane.

    4. Rubbery wound closure adhesives. II. initiators for and initiation of 2-octyl cyanoacrylate polymerization

      Istvan Szanka, Amalia Szanka and Joseph P. Kennedy

      Article first published online: 28 MAR 2015 | DOI: 10.1002/pola.27605

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      Methodologies were developed to measure initiator reactivity of neat OctCA polymerizations induced by select N bases. Polymerizations are very rapid and exothermic upon contact with Et3N, ABCO and DABCO, and Pyr, and much slower with DMT initiator. Overall rates are faster using initiators dissolved in THF than in toluene indicating polarity effects.Relative initiator reactivity is discussed in terms of structural considerations.

    5. Synthesis, characterization, and photocuring of siloxane-oxirane monomers

      Fernanda B. Leal, Claudio M. Pereira and Fabrício A. Ogliari

      Article first published online: 28 MAR 2015 | DOI: 10.1002/pola.27616

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    6. Silafluorene-based polymers for electrochromic and polymer solar cell applications

      Ozan Erlik, Naime A. Unlu, Gonul Hizalan, Serife O. Hacioglu, Seda Comez, Esra D. Yildiz, Levent Toppare and Ali Cirpan

      Article first published online: 28 MAR 2015 | DOI: 10.1002/pola.27625

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      Four new silafluorene and benzotriazole bearing conjugated copolymers were synthesized. These polymers are promising both for electrochromic devices and polymer solar cell applications. All of the polymers are ambipolar and multichromic. Power conversion efficiency of the polymer solar cell reached 1.75% for PTBTSiF, 1.55% for PSBSSiF, 2.57% for PBTBTSiF and 1.82% for PBSBSSiF. The hole mobilities of the polymers are estimated through space charge limited current (SCLC) model. PBTBTSiF has the highest hole mobility as 2.44x10−3 cm2/Vs.

    7. One-pot synthesis of terpolymers with long l-lactide rich sequence derived from propylene oxide, CO2, and l-lactide catalyzed by zinc adipate

      Lei Tang, Wenhan Luo, Min Xiao, Shuanjin Wang and Yuezhong Meng

      Article first published online: 28 MAR 2015 | DOI: 10.1002/pola.27617

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      The terpolymer derived from CO2, PO, and l-Lactide (LLA) with long LLA sequence can be efficiently synthesized via one-step, one-pot methodology by utilizing zinc adipate as catalyst. The introduction of the comonomer l-LA could not only increase the polycarbonate yield, but also significantly improve the thermal stability and mechanical properties.

    8. Synthesis and characterization of novel fluorosilicone rubber using imide modified vinyl-containing fluorosilicone resin as cross-linker

      Tao Xu, He Liu, Jie Song, Shibin Shang, Zhanqian Song, Kaifei Zou and Chong Yang

      Article first published online: 28 MAR 2015 | DOI: 10.1002/pola.27619

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      A novel imide modified vinyl fluorosilicone resin was synthesized from the natural rosin derivative (maleopimaric acid). With this resin as a new crosslinker in common heat curable fluorosilicone rubber composition, a series of imide-modified fluorosilicone rubbers were obtained and characterized. When the loading of new crosslinker is 2.0 wt %, compared with ordinary fluorosilicone rubber, the tearing strength of obtained fluorosilicone rubber increases by 23.5%, breaking elongation by 18.6% and rebound resilience by 9.7%.

    9. Synthesis and characterization of polyphenylenes with polypeptide and poly(ethylene glycol) side chains

      Huseyin Akbulut, Takeshi Endo, Shuhei Yamada and Yusuf Yagci

      Article first published online: 28 MAR 2015 | DOI: 10.1002/pola.27621

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      Two novel strategies to obtain PPP polymers bearing PEG and poly-l-lysine (PLL) side chains are presented: (1) Suzuki coupling polymerization between PEG and polypeptide macromonomers, and (2) NCA graft polymerization over the PPP backbone bearing the primary amine and PEG groups. The approaches are comprised of the combination of Suzuki coupling and in situ N-carboxyanhydride (NCA) ring-opening polymerization (ROP) processes. Polypeptide macromonomer was prepared by ROP of the corresponding NCA precursor using (2,5-dibromophenyl)methanamine as an initiator.

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      Self-emulsion polymerization of baylis–hillman-derived α-hydroxymethyl-substituted acrylates

      Chao Peng and Abraham Joy

      Article first published online: 28 MAR 2015 | DOI: 10.1002/pola.27623

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      Amphiphilic alkyl α-hydroxymethyl acrylates can be polymerized via self-emulsion polymerization (i.e., without surfactants) under conventional radical and reversible addition-fragmentation chain transfer polymerization conditions. The α-hydroxymethyl acrylates can be copolymerized at very low percentages (∼5%) with conventional monomers such as butyl acrylate under surfactant free conditions. The hydroxyl group of the α-hydroxymethyl acrylates in the resultant latex could potentially be used for further functionalization or for modulation of surface properties.

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      Synthesis of linear cucurbit[7]uril pendent copolymers through radical polymerization: Polymers with ultra-high binding affinity

      Hao Chen, Haili Ma and Yebang Tan

      Article first published online: 28 MAR 2015 | DOI: 10.1002/pola.27624

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      Cucurbiturils are a series of macrocyclic molecules with high binding affinity. A universal method for the synthesis of cucurbit[7]uril (CB[7]) pendent linear copolymers through free radical copolymerization is presented. CB[7] was firstly grafted with mono-(4-vinylbenzyl) group and then copolymerized with acrylamide based monomers to obtain the desired CB[7] pendent linear copolymers. The copolymers inherit CB[7]'s high binding affinity to guest molecules and they can achieve extremely high binding affinity (over 1012 M−1) with amantadine hydrochloride.

  5. Articles

    1. Synthesis and characterization of polyaniline nanoparticles in phosphonic acid amphiphile aqueous micellar solutions for waterborne corrosion protection coatings

      F. X. Perrin, T. A. Phan and D. L. Nguyen

      Article first published online: 25 MAR 2015 | DOI: 10.1002/pola.27602

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      It is demonstrated that long-chain alkyl phosphonic acids are promising surfactants for the preparation of stable polyaniline dispersions with high potentials for application in corrosion protection. The high conductivity (3.6 S cm−1) and enhanced solubility is related to the formation of layered structure of PANI backbone separated by alkyl side chains of DPA. The excellent corrosion resistance of steel offered by DPA-PANI is due to the smart release of DPA when damage is produced on the surface of the coating.

    2. Polymerization via the Ugi-reaction using aromatic monomers

      Niklas Gangloff, Daniel Nahm, Lisa Döring, Dirk Kuckling and Robert Luxenhofer

      Article first published online: 25 MAR 2015 | DOI: 10.1002/pola.27610

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      The highly modular Ugi four-component reaction is used to directly obtain polymers from aromatic monomer of high molar mass. This approach allows facile access to highly complex, sequence-specific functional polymers.

    3. Donor–acceptor semiconducting polymers based on pyromellitic diimide

      Ruvini S. Kularatne, Prakash Sista, Harsha D. Magurudeniya, Jing Hao, Hien Q. Nguyen, Michael C. Biewer and Mihaela C. Stefan

      Article first published online: 25 MAR 2015 | DOI: 10.1002/pola.27607

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      Three donor–acceptor polymers P1, P2, and P3 with N,N′-dodecylpyromellitic diimide as the electron-acceptor unit with three diethynyl-substituted donor monomers: 1,4-diethynyl-2,5-bis(octyloxy)benzene, 2,7-diethynyl-9,9-dioctyl-9H-fluorene, and 3,3′-didodecyl-5,5′-diethynyl-2,2′-bithiophene, were synthesized. In the presence of PC61BM acceptor, these three polymers undergo fluorescence quenching, indicating the intermolecular photo-induced charge transfer between the donor and the acceptor moieties.

    4. Star polymers by photoinduced copper-catalyzed azide–alkyne cycloaddition click chemistry

      Hatice Busra Tinmaz, Irem Arslan and Mehmet Atilla Tasdelen

      Article first published online: 25 MAR 2015 | DOI: 10.1002/pola.27612

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      For environmental and practical issues, a simple and efficient photoinduced CuAAC process is applied for a series of star polymers including star polymers containing three-, four-, and eight-arms. Spectroscopic and chromatographic investigations reveal that successful macromolecular syntheses have been achieved under mild conditions.

    5. Novel panchromatic photopolymerizable matrices: N,N'-dibutylquinacridone as an efficient and versatile photoinitiator

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

      Article first published online: 25 MAR 2015 | DOI: 10.1002/pola.27615

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      N,N'-dibutylquinacridone (DBQA) is utilized here for the first time as a high-performance panchromatic photoinitiator for the cationic polymerization (CP) of epoxides, the free radical polymerization (FRP) of acrylates, the thiol-ene polymerization and the synthesis of interpenetrated polymer networks (epoxide/acrylate) under violet, blue, green and yellow lights. It confers a remarkable panchromatic character to the photopolymerizable matrices.

    6. Facile synthesis of polyester dendrimer via combining thio-bromo “Click” chemistry and ATNRC

      Xiaoshan Fan, Zhiguo Hu and Guowei Wang

      Article first published online: 25 MAR 2015 | DOI: 10.1002/pola.27618

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      An efficient synthesis approach to aliphatic polyester dendrimer, poly(thioglycerol-2-propionate) (PTP) was developed by combination of thio-bromo “click” chemistry with atom transfer nitroxide radical coupling (ATNRC). First, repeating units were divergently grown from the end of PS support and the resulting intermediates l-PS-d-PTP (G1-G4) can be easily purified by a simple precipitation in ethanol. Finally, the PTP G-4 was obtained by cleaving the alkoxyamine group at elevated temperature (125 °C).

    7. Synthesis of maltopentaose-conjugated surface-active styrenic monomers and their micellar homopolymerization in water

      Daichi Togashi, Issei Otsuka, Redouane Borsali, Atsushi Narumi and Seigou Kawaguchi

      Article first published online: 23 MAR 2015 | DOI: 10.1002/pola.27609

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      A versatile method to prepare maltopentaose (Mal5)-conjugated surface-active styrenic monomers has been developed and their physicochemical parameters were listed. The glycomonomer with high surface-active properties was shown to predominately generate the micelles with worm-like morphologies. Radical homopolymerizations of the glycomonomers provided a significant result that the glycomonomer forming the worm-like micelles showed a very high polymerizability.

    8. RAFT radical copolymerization of beta-pinene with maleic anhydride and aggregation behaviors of their copolymer in aqueous solution

      Yi Wang, Qianxiang Ai and Jiang Lu

      Article first published online: 23 MAR 2015 | DOI: 10.1002/pola.27601

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      A novel block copolymer poly(beta-pinene-alt-maleic anhydride)-b-polystyrene was synthesized based on the living/controlled radical alternating copolymerization. By hydrolyzing this block copolymer, a pH-sensitive amphiphilic block copolymer poly(beta-pinene-alt-maleic acid)-b-polystyrene was formed, and it would self-assemble into nano-micelles in aqueous solution with different morphology determined by the pH value.

    9. Poly(p-benzamide) having isopropyl-substituted chiral tri(ethylene glycol) side Chain: Synthesis and helical conformation

      Akihiro Yokoyama, Suguru Nakano, Tomoaki Saiki and Tsutomu Yokozawa

      Article first published online: 23 MAR 2015 | DOI: 10.1002/pola.27608

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      To increase the difference of stability between right- and left-handed helical structures, isopropyl-substituted tri(ethylene glycol) is used as a chiral side chain of N-substituted poly(p-benzamide). The target polymer is synthesized by chain-growth condensation polymerization. The CD study of the polymer reveals that the replacement of the methyl group with a bulkier isopropyl group at the side chain of poly(p-benzamide) increased the ratio of a one-handed helical structure.

    10. Synthesis of bithiazole-based crystalline polymers via palladium-catalyzed direct C[BOND]H arylation

      Wei Lu, Junpei Kuwabara, Masahiro Kuramochi and Takaki Kanbara

      Article first published online: 23 MAR 2015 | DOI: 10.1002/pola.27611

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      A direct arylation polycondensation affords a bithiazole-based homopolymer and donor–acceptor-type copolymers where the bithiazole unit served as an electronic acceptor. The obtained polymers are highly crystalline owing to the strong interchain interactions of the bithiazole units and the electrostatic interactions of the donor–acceptor structures. The flexible alkyl chains are necessary to achieve a highly ordered structure.

    11. In situ synthesis of ABA triblock copolymer nanoparticles by seeded RAFT polymerization: Effect of the chain length of the third a block on the triblock copolymer morphology

      Haijiao Kang, Yang Su, Xin He, Shifeng Zhang, Jianzhang Li and Wangqing Zhang

      Article first published online: 23 MAR 2015 | DOI: 10.1002/pola.27620

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      Seeded RAFT polymerization based on the nanoparticles of the PDMA-b-PS diblock copolymer is investigated. This seeded RAFT polymerization affords the in situ synthesis of the core-corona nanoparticles of the PDMA-b-PS-b-PDMA triblock copolymer, in which the middle solvophobic PS block forms the compacted core, and the first solvophilic PDMA block and the introduced third PDMA block form the solvated complex corona.

    12. Synthesis of biodegradable conjugated polymers with controlled backbone flexibility

      Tereza Vokatá, Megan Twomey, Eladio Mendez and Joong Ho Moon

      Article first published online: 23 MAR 2015 | DOI: 10.1002/pola.27622

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      A series of PPE copolymers with variable flexible content was prepared using modified Sonogashira coupling conditions. Despite breaks in conjugation induced by the flexible component, polymers with less than 50% of flexible linker exhibited fluorescence properties comparable to those of a fully conjugated PPE backbone. The self-assembly behaviors of the corresponding nanoparticles were clearly different among the rigid and flexible polymers upon polyanion complexation.

    13. Minimization of the auxiliary reagent loading for direct arylation polymerization (DArP) of 2-bromo-3-hexylthiophene

      Andrey E. Rudenko, Alia A. Latif and Barry C. Thompson

      Article first published online: 21 MAR 2015 | DOI: 10.1002/pola.27581

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      The necessary loading of auxiliary reagents for direct arylation polymerization (DArP) is successfully minimized to use only 313 ppm loading of palladium acetate (the lowest catalyst loading reported so far for the synthesis of conjugated polymers via DArP) and 3.75% of neodecanoic acid while producing poly(3-hexylthiophene) with high molecular weight and in high yield. Examination of polymer chemical structure confirms increased regioregularity and the absence of branching defects, which translate into attractive polymer properties.

    14. Polymer coating of graphene oxide via reversible addition–fragmentation chain transfer mediated emulsion polymerization

      Vien T. Huynh, Duc Nguyen, Christopher H. Such and Brian S. Hawkett

      Article first published online: 21 MAR 2015 | DOI: 10.1002/pola.27596

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      This work describes a versatile method to encapsulate graphene oxide (GO) with polymers using RAFT mediated emulsion polymerization. TEM, SEM, FTIR, and AFM were used to confirm the presence of the polymer layer on the surface of the GO. The thickness of the polymer coating can be adjusted by controlling the amount of monomer fed into the system. Partial polymer coatings of the GO could be achieved by varying the amount of poly(allylamine hydrochloride).

    15. Synthesis and characterization of hyperbranched amphiphilic block copolymers prepared via self-condensing RAFT polymerization

      Maria Rikkou-Kalourkoti, Marios Elladiou and Costas S. Patrickios

      Article first published online: 21 MAR 2015 | DOI: 10.1002/pola.27574

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      Reversible addition-fragmentation chain transfer polymerization (RAFT) together with an inimer were employed to prepare hyperbranched amphiphilic block copolymers of styrene (Sty) and 2-vinylpyridine (2VPy) or 4-vinylpyridine (4VPy). While both addition sequences were applied, better control of the polymer structure was achieved when the VPy monomers were polymerized first. Aminolysis of the hyperbranched polymers resulted in linear polymers with lower molecular weights and dispersity than the parent polymers. Finally, it was found that the prepared hyperbranched copolymers self-assembled in selective solvents.

    16. Synthesis and characterization of thermoplastic elastomers with polyisobutylene and polyalloocimene blocks

      Attila L. Gergely and Judit E. Puskas

      Article first published online: 21 MAR 2015 | DOI: 10.1002/pola.27587

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      Polyisobutylene-based thermoplastic elastomers were successfully synthesized using a renewable monomer, alloocimene, to construct the glassy segments. Triblock and tetrablock copolymers are prepared by the sequential monomer addition technique using the butyl polymerization system (H2O/AlCl3 in MeCl at −95 °C). The new materials exhibit similar mechanical properties to thermoplastic elastomers with hard blocks of polystyrene and its derivatives, with the added advantage of using an inexpensive two-phase living cationic polymerization system. The structure–property relationships are also discussed.

    17. Influence of 4-fluorophenyl pendants in thieno[3,4-b]thiophene-benzo[1,2-b:4,5-b′]dithiophene-based polymers on the performance of photovoltaics

      Tomoyuki Yamamoto, Tomoyuki Ikai, Shinji Katori, Takayuki Kuwabara, Katsuhiro Maeda, Tomoyuki Koganezawa, Kohshin Takahashi and Shigeyoshi Kanoh

      Article first published online: 19 MAR 2015 | DOI: 10.1002/pola.27589

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      Polymers consisting of benzo[1,2-b:4,5-b′]dithiophene and thieno[3,4-b]thiophene units, either fully or partially containing 4-fluorophenyl pendants, have been synthesized as electron donors for inverted-type polymer solar cells (PSCs). Incorporation of 4-fluorophenyl pendants into the polymers affected the frontier orbitals, the hole mobilities, crystallinity, orientation, and compatibility with an electron acceptor in the active layers. The incorporation of an appropriate number of 4-fluorophenyl pendants enhanced the power conversion efficiencies of the PSC devices from 2.25 to 3.96%.

    18. Facile preparation of highly conductive, flexible, and strong carbon nanotube/polyaniline composite films

      Hong-Mei Xiao, Wei-Dong Zhang, Li Na, Gui-Wen Huang, Yu Liu and Shao-Yun Fu

      Article first published online: 18 MAR 2015 | DOI: 10.1002/pola.27588

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      A highly conductive, flexible, and strong carbon nanotube/polyaniline composite film prepared via a facile solvent-evaporation has been obtained by a cold stretching. The maximum value of the composite conductivity (ca. 231 S/cm) in the stretching direction is achieved at the elastic limit stress. Meanwhile, the strength is moderately improved over that of the pure PANI film and the flexibility is maintained to a high degree by the addition of the 2 wt % CNTs.

    19. Water-soluble cationic polypyrrole based probe for fluorometric and voltammetric detection of base pair mismatched oligonucleotides

      Jiangna Guo, Jie Zhao, Bin Wang and Feng Yan

      Article first published online: 16 MAR 2015 | DOI: 10.1002/pola.27595

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      The synthesized cationic polypyrrole, poly(N-(4-butyl-(1-methylimidazole)) pyrrole bromide) (PNBMIP-Br), was used for base pair mismatched oligonucleotides detection. The electrostatic attraction and fluorescence resonance energy transfer of PNBMIP-Br/DNA complexes resulted in an amplification and effective recognition of the fluorescence signals. Cyclic voltammogram was proved to be an effective method to distinguish ss-DNA and ds-DNA.

    20. Crosslinked poly(ethylene oxide) containing siloxanes fabricated through thiol-ene photochemistry

      Victor A. Kusuma, Elliot A. Roth, William P. Clafshenkel, Steven S. Klara, Xu Zhou, Surendar R. Venna, Erik Albenze, David R. Luebke, Meagan S. Mauter, Richard R. Koepsel, Alan J. Russell, David Hopkinson and Hunaid B. Nulwala

      Article first published online: 16 MAR 2015 | DOI: 10.1002/pola.27594

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      Crosslinked homogeneous amphiphilic polymer films containing poly(ethylene oxide) and polysiloxane functionality can be readily fabricated using UV curing. The films show promise in applications requiring biocompatibility and are also promising as membranes for industrial CO2 separation.

    21. Syntheses of biphenyl-terminated polyhedral oligomeric octasilicate-core dendrimers and their single-component optical transparent free-standing thermoplastic films

      Yasuyuki Irie and Kensuke Naka

      Article first published online: 16 MAR 2015 | DOI: 10.1002/pola.27583

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      2-Biphenylethyl and 2-biphenylhexyl-terminated polyhedral oligomeric octasilicate (OS)-core polyester-typed dendrimers, denoted as OS-C2-BP and OS-C6-BP, respectively, were prepared and their bulk properties were studied. OS-C2-BP formed a transparent film, whereas OS-C6-BP formed an opaque whitish waxy film. The coating film of OS-C2-BP was easily peeled off from a substrate and formed a free-standing film. The results of X-ray diffraction (XRD) and differential scanning calorimeter (DSC) suggest that the film of OS-C2-BP was amorphous, whereas the film of OS-C6-BP contained a crystalline domain.

    22. Synthesis and characterization of soft–hard stereoblock polybutadiene with Fe(2-EHA)3/Al(i-Bu)3/DEP catalyst system

      Wenjie Zheng, Feng Wang, Jifu Bi, Hexin Zhang, Chunyu Zhang, Yanming Hu, Chenxi Bai and Xuequan Zhang

      Article first published online: 12 MAR 2015 | DOI: 10.1002/pola.27533

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      Stereoblock polybutadiene (PBD), composed of amorphous equibinary cis−1,4/1,2 PBD (e-PBD) and crystalline syndiotactic 1,2-PBD (s-1,2-PBD) segments, is synthesized through one-pot sequential polymerization with an iron(III)2-ethylhexanoate/triisobutylaluminum/diethyl phosphate catalyst system. The change in stereoselectivity and regioselectivity is achieved by the addition of excess AlR3 and a second feed of the monomer, which is a facile and efficient method to prepare the stereoblock PBD for the first time.

    23. Imino(phenoxide) compounds of magnesium: Synthesis, structural characterization, and polymerization studies

      Swarup Ghosh, Debashis Chakraborty and Venkatachalam Ramkumar

      Article first published online: 5 MAR 2015 | DOI: 10.1002/pola.27579

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      The first example of a monomeric magnesium catalyst systemfor the copolymerization of styrene dioxide and CO2is reported. All the catalysts also show good catalytic activity toward the copolymerization of CO2 with cyclohexene oxide and styrene oxide. The overall process is green and eco-friendly since magnesium is biocompatible and these polymers are biodegradable.

    24. Novel pendent thiophene side-chained benzodithiophene for polymer solar cells

      Ruiying Sheng, Qian Liu, Manjun Xiao, Chunyang Gu, Tong Hu, Junzhen Ren, Mingliang Sun and Renqiang Yang

      Article first published online: 5 MAR 2015 | DOI: 10.1002/pola.27585

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      Two novel pendent thiophene (2-butyl-5-octylthiophene) side-chained BDT- and TPD- based polymers were successfully synthesized. BDT with pendent thiophene and ethylhexyl (EH) side-chained TPD-based polymer shows relatively low-lying HOMO energy level (−5.52 eV) with the help of some other side groups on copolymerization unit and nearly 1 V high open circuit voltage (VOC) which is the highest VOC achieved by BDT- and TPD-based polymers.

    25. pH- and β-cyclodextrin-responsive micelles based on polyaspartamide derivatives as drug carrier

      Huan Yu, Jian Sun, Yunti Zhang, Guangyan Zhang, Yanfeng Chu, Renxi Zhuo and Xulin Jiang

      Article first published online: 5 MAR 2015 | DOI: 10.1002/pola.27584

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      A novel polyaspartamide-based graft polymer containing acid-labile benzoic imine linkage and adamantine groups in the side chains was fabricated for drug delivery, which can self-assemble into polymeric micelles showing pH- and β-cyclodextrin responsiveness. The doxorubicin-loaded micelles are stable under physiological conditions exhibiting a rapid release under acidic or β-cyclodextrin environment, which displayed comparative anticancer activity to free doxorubicin, whereas blank polymeric micelles were nontoxic.

    26. Reversible addition-fragmentation chain transfer polymerization of vinyl acetate under high pressure

      Jing Chen, Xiaoning Zhao, Lifen Zhang, Zhenping Cheng and Xiulin Zhu

      Article first published online: 5 MAR 2015 | DOI: 10.1002/pola.27582

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      Well-defined PVAc with high molecular weight and narrow molecular weight distribution can be obtained relatively fast by using RAFT polymerization at 5 kbar.

    27. Thermoresponsive PNIPAM/silica nanoparticles by direct photopolymerization in aqueous media

      Hua Zou and Helmut Schlaad

      Article first published online: 5 MAR 2015 | DOI: 10.1002/pola.27593

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      A simple and facile method to fabricate thermoresponsive polymer-grafted silica particles by direct surface-initiated photopolymerization of N-isopropylacrylamide (NIPAM) is presented. This method is based on silica particles bearing with thiol functionalities, which are transformed into thiyl radicals by irradiation with UV light to initiate the polymerization of NIPAM at room temperature. Immobilization of a photoinitiator and/or use of additional initiator are not needed, and the photopolymerization can be conducted in aqueous media.

    28. Dispersion of silica nanoparticles bearing perfluorohexyl units into fluorinated copolymers

      Nelly Durand, Jean-Pierre Habas, Bernard Boutevin and Bruno Améduri

      Article first published online: 5 MAR 2015 | DOI: 10.1002/pola.27586

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      The modification of silica nanoparticles by radical addition of C6F13I and C6F13-C2H4-SH led to various fluorinated silica of surface hydrophobies 143° and 124°. The dispersion of these fillers into molten poly(VDF-co-HFP) and poly(TFE-co-HFP) matrices, as well as the hydrophobic, mechanical, and thermal properties of both fluorinated copolymers and the resulting composites, were studied.

    29. Synthesis of diisocyanides with phenolic groups and their polymerization to helically chiral poly(quinoxaline-2,3-diyl)s

      Johannes Scholz and Michael Reggelin

      Article first published online: 4 MAR 2015 | DOI: 10.1002/pola.27580

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      The synthesis of new diisocyanide monomers with one or two phenolic groups is described. Their polymerization ability is affected mainly by steric crowding of the diisocyanide functions by adjacent groups. With a chiral Pd-initiator a helix-sense selective polymerization is achieved and deprotection is done successfully. The obtained optically active polymers with Brønsted functionalities in each repeating unit are thought as chiral, reusable organocatalysts.

    30. Synthesis and optical properties of σ–π conjugated organic–inorganic hybrid gels

      Naofumi Naga, Hitomi Nagino, Midori Iwashita, Tomoharu Miyanaga and Hidemitsu Furukawa

      Article first published online: 4 MAR 2015 | DOI: 10.1002/pola.27571

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      Organic–inorganic hybrid gels containing Si-vinylene units have been synthesized by a hydrosilylation reaction of tri- or tetra-ethynyl aryl compounds, TEB, TEBP, or TEPM, and bisdimethylsilyl compounds, TMDS or BDMSB, in toluene. The reactions yielded the gels having homogeneous network structure of 1.5–2.9 nm mesh size under the monomer concentrations that were relatively higher than the critical gelation concentration. The gels showed emission in the ranged from 350 to 500 nm.

    31. Optimizing the electrochemical performance of imidazolium-based polymeric ionic liquids by varying tethering groups

      Zhe Jia, Wen Yuan, Chunjuan Sheng, Hui Zhao, Heyi Hu and Gregory L. Baker

      Article first published online: 4 MAR 2015 | DOI: 10.1002/pola.27567

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      The synthesis and characterization of novel imidazolium-based ionic liquid (IL) model compounds and corresponding polymeric ionic liquidILs (PILs) with various tethering groups were reported. Poly(ethylene oxide) (PEO) repeating units were attached as tethering groups to the imidazolium cation to optimize the glass transition temperatures (Tg) and ionic conductivities of the PILs. The novel PILs exhibit excellent conductivity. The thermophysical and electrochemical properties of ILs, including thermal transition, ionic conductivity, and rheological behavior, were characterized.

    32. Screening of metal catalysts influence on the synthesis, structure, properties, and biodegradation of PLA-PBA triblock copolymers obtained in melt

      Anna Kundys, Andrzej Plichta, Zbigniew Florjańczyk, Anita Frydrych and Konrad Żurawski

      Article first published online: 4 MAR 2015 | DOI: 10.1002/pola.27576

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      Triblock copolymers comprising poly(1,4-butylene adipate) segment and polylactidearmswere obtained under technological conditions. Acetylacetonates of Li, Mg, Ca, Zn, Fe, and Zr were used as catalysts. The macroinitiator is incorporated into the major products; however, linear and cyclic homopolymers and copolymers are present. The efficiency of side reactions, including racemization of polylactide, depends on the catalyst used. The copolymers studied undergo faster biodegradation than polylactide and they can decompose in compost within 16 weeks.

  6. Rapid Communication

    1. K+ responsive supramolecular polymer constructed by dibenzo-30-crown-10/paraquat-based molecular recognition

      Rener Chen, Qizhong Zhou, Bin Zhang, Jiashou Wu, Yuyuan Ye, Guoliang Dai and Huajiang Jiang

      Article first published online: 3 MAR 2015 | DOI: 10.1002/pola.27569

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      A supramolecular polymer constructed by dibenzo-30-crown-10/paraquat-based molecular recognition is reported. Owing to the responsiveness and reversibility of the dibenzo-30-crown-10/paraquat host−guest interactions, the reversible transition between the linear supramolecular polymer and monomers was achieved by adding K+ and DB18C6.

  7. Articles

    1. Control of chain ends of polyesters in polycondensation of AA and BB monomers by use of solid-phase reagent

      Toshihiko Sugiura, Daisuke Yajima, Kento Shoji, Yoshihiro Ohta and Tsutomu Yokozawa

      Article first published online: 3 MAR 2015 | DOI: 10.1002/pola.27573

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      For selective synthesis of linear polyester having a functional group at one end by polycondensation of AA and BB monomers, diol and diacid chloride are reacted in the presence of oxime resin or silica gel, followed by aniline-mediated cleavage of the oxime ester moiety, through which the formed polyester is connected to the support, to afford polyester with anilide at one end together with polyester with anilides at both ends.

    2. 1-(2,6-dibenzhydryl-4-fluorophenylimino)-2-aryliminoacenaphthylylnickel halides highly polymerizing ethylene for the polyethylenes with high branches and molecular weights

      Linlin Fan, Shizhen Du, Cun-Yue Guo, Xiang Hao and Wen-Hua Sun

      Article first published online: 3 MAR 2015 | DOI: 10.1002/pola.27572

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      The 1-(2,6-dibenzhydryl-4-fluorophenylimino)-2-aryliminoacenaphthylylnickel halides, activated with methylaluminoxane, show high activities toward ethylene polymerization, producing polyethylenes with high branches and molecular weights as well as narrow polydispersity.

    3. Polymeric nanocomposite comprising gold nanoparticles and bilaterally sulfur-functionalized polystyrene

      Ying-Shian Liou, Hsin-Chih Tsai, Cheng-Yang Yeh and Raymond Chien-Chao Tsiang

      Article first published online: 3 MAR 2015 | DOI: 10.1002/pola.27562

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      A bilaterally sulfur-functionalized polystyrene, was synthesized anionically and used to make a polystyrene/gold nanoparticles (AuNPs) nanocomposite with AuNPs formed in situ in polymer solution through reduction of AuClO4.This polymer exhibits better particle-dispersing capability and results in a smaller AuNPS size than an unilaterally thiomethyl-functionalized PS. The composite comprising a bilateral functionalized polymer hasa higher Tg than that comprising an unilaterally functionalized polymer.

  8. Rapid Communication

    1. You have free access to this content
      Photobase generators derived from trans-o-coumaric acid for anionic UV curing systems without gas generation

      Koji Arimitsu, Yuri Takemori, Atsushi Nakajima, Ayaka Oguri, Masahiro Furutani, Takahiro Gunji and Yoshimoto Abe

      Article first published online: 3 MAR 2015 | DOI: 10.1002/pola.27552

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      Anionic UV curing systems of poly(glycerol methacrylate) and/or poly[3-(methacryloyloxy)propyltrimethoxysilane] is achieved using novel photobase generators (PBGs) derived from trans-o-coumaric acid. These PBGs are decomposed into amines and coumarins by UV irradiation without generation of gases that cause cracks and bubbles in cured films.

  9. Articles

    1. Fluorous solvent-soluble imaging materials containing anthracene moieties

      Hye-Jin Park, Heeyoung Jung, Soo-Hyun Kim, Myeongjin Park, Ji-Hoon Kim, Jongchan Son, Byung Jun Jung, Do-Hoon Hwang, Changhee Lee, Jin-Kyun Lee, Jong Geun Yoon and Soo Young Yoon

      Article first published online: 3 MAR 2015 | DOI: 10.1002/pola.27561

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      Fluorous solvent-soluble, photoreactive polymers were designed using a photodimerization chemistry of anthracene moieties. Four random copolymers with Mn = 20,000–27,000 were synthesized, involving an anthracene-containing monomer and a fluorinated methacrylate with varying compositions. The polymers showed sufficient solubility in the fluorous solvents but were rendered insoluble by UV irradiation. One of the copolymers, FSIM-2, recognized itself as a promising photoreactive imaging material for the photolithographic patterning of OLED pixels.

    2. Low band-gap diketopyrrolopyrrole-containing polymers for near infrared electrochromic and photovoltaic applications

      Jonathan Zhaozhi Low, Wei Teng Neo, Qun Ye, Wen Jie Ong, Ivy Hoi Ka Wong, Ting Ting Lin and Jianwei Xu

      Article first published online: 3 MAR 2015 | DOI: 10.1002/pola.27564

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      Electrochromic conjugated polymers derived from diketopyrrolopyrrole and 3,4-ethylenedioxythiophene exhibit strong and broad absorption with a maximum of about 830 nm in the near infrared region in their neutral film states. Upon applying for a voltage, the polymers change their colors between dark green and light blue with contrasts in the NIR regions of up to 78 and 63% as thin films and single-layer electrochromic devices, respectively.

    3. Synthesis and properties of renewable nonisocyanate polyurethanes (NIPUs) from dimethylcarbonate

      Charlotte Duval, Nasreddine Kébir, Agathe Charvet, Amélie Martin and Fabrice Burel

      Article first published online: 3 MAR 2015 | DOI: 10.1002/pola.27568

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      Novel fully renewable NIPUs are prepared from diamines, diols, and dimethylcarbonate using the transurethanization as a green, straightforward and sustainable approach.

    4. Facile synthesis of thermosensitive functional polyaspartamide derivatives by click chemistry

      Guangyan Zhang, Yunti Zhang, Yanfeng Chu, Yingying Ma, Renxi Zhuo and Xulin Jiang

      Article first published online: 3 MAR 2015 | DOI: 10.1002/pola.27566

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      Facile synthesis of functional stimuli-responsive polymers with polyaspartamide backbone containing pendant aromatic structures or imidazole rings via click reaction is described. The graft reaction efficiency is very high above 90%. The thermoresponsive behavior of obtained polymers may be tuned by designed amounts of azide groups and graft percentage of hydrophobic moieties and can be further functionalized with hydrophilic long PEG chain and/or targeted moieties via click chemistry for drug delivery.

    5. Complexation of dodecyl-substituted poly(acrylate) by linked β-cyclodextrin dimers and trimers in aqueous solution

      Duc-Truc Pham, Hanh-Trang Nguyen, Stephen F. Lincoln, Jie Wang, Xuhong Guo, Christopher J. Easton and Robert K. Prud'homme

      Article first published online: 3 MAR 2015 | DOI: 10.1002/pola.27563

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      The host-guest complexation by β-cyclodextrin, β-CD, and the β-CD groups of the linked β-CD dimers, β-CD2ur and β-CD2su and trimers, β-CD3bz and β-CDen3bz, of the dodecyl, C12, substituents of the 3.0% substituted poly(acrylate), PAAC12, in dilute aqueous solution exhibits substantial variations in the associated complexation constants and ΔH and TΔS changes arising from structural differences in the complexes formed. In more concentrated solutions, differences in viscosity are also attributable to structural differences.

    6. Synthesis of high thermal stability polybenzoxazoles via Ortho-imide-functional benzoxazine monomers

      Kan Zhang, Jia Liu, Seishi Ohashi, Xiaoyun Liu, Zhewen Han and Hatsuo Ishida

      Article first published online: 27 FEB 2015 | DOI: 10.1002/pola.27565

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      A series of imide functional benzoxazine resins were synthesized as precursors for producing cross-linked polyimide. In addition to polymerization of forming cross-linked polyimide, the ortho-imide functional benzoxazine resins can undergo a further smart route to form a more thermally stable cross-linked polybenzoxazole by releasing carbon dioxide. The ortho-imide functional benzoxazine resins show the possibility to form high performance thermosets with low cost and easy processability.

    7. Investigation of Suzuki–Miyaura catalyst-transfer polycondensation of AB-type fluorene monomer using coordination-saturated aryl Pd(II) halide complexes as initiators

      Zilong Zhang, Pan Hu, Xiao Li, Hongmei Zhan and Yanxiang Cheng

      Article first published online: 27 FEB 2015 | DOI: 10.1002/pola.27577

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      Stable aryl Pd(II) halide complexes with auxiliary ligands PCy3 and P(o-tol)3 were successfully synthesized by direct oxidative addition of aryl halide to the corresponding Pd(0) precursors and achieved the catalyst-transfer polymerization to afford the well-defined polymers with triarylamine/H end groups. The complex with P(o-tol)3 has higher activity in the process of Suzuki–Miyaura catalyst-transfer polycondensation, which is comparable with the classical Pd(II) initiator ligated by P(tBu)3.

    8. Suppressing the long-chain branching in the synthesis of poly(styrene-b-butyl acrylate-b-styrene) in RAFT emulsion polymerization by tuning the interfacial properties

      Yunlong Guo, Xiang Gao and Yingwu Luo

      Article first published online: 27 FEB 2015 | DOI: 10.1002/pola.27578

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      In the synthesis of polystyrene-b-poly(n-butyl acrylate)-b-polystyrene triblock copolymer via reversible addition-fragmentation chain transfer emulsion polymerization, PDI is broadened by the formation of long-chain branches (LCBs) during the formation of the third block. Decreasing the interfacial transport resistance suppresses LCB formation, narrowing PDI.

    9. Effect of branched alkyl side chains on the performance of thin-film transistors and photovoltaic cells fabricated with isoindigo-based conjugated polymers

      Gi Eun Park, Jicheol Shin, Dae Hee Lee, Min Ju Cho and Dong Hoon Choi

      Article first published online: 21 FEB 2015 | DOI: 10.1002/pola.27555

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      New isoindigo and di(thienyl)ethylene-containing conjugated polymers with different branched side chains were successfully synthesized. PIDTE-S6 polymer bearing 11-heptyltricosane side chains showed much better charge transport behavior (µ = 4.07 cm2 V−1 s−1) than those of PIDTE-S3 with 11-butyltricosane side chains. In contrast, bulk heterojunction organic photovoltaic cells made from a blend film of PIDTE-S3 and PC61BM demonstrated promising device performance with a power conversion efficiency in the range of 4.9–5.0%.

    10. Preparation of photocrosslinked sol-gel composites based on urethane-acrylic matrix, silsesquioxane sequences, TiO2, and Ag/Au NPs for use in photocatalytic applications

      Andreea L. Chibac, Violeta Melinte, Tinca Buruiana, Ionel Mangalagiu and Emil C. Buruiana

      Article first published online: 21 FEB 2015 | DOI: 10.1002/pola.27548

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      The preparation of hybrid materials, incorporating titania and silsesquioxane units, achieved through the sol–gel and photopolymerization processes, together with photoinduced formation of noble metallic nanoparticles (Ag/Au) in polymer networks for eco-friendly photocatalysts, is reported.

    11. Base-amplifying silicone resins with photobase-generating side chains and their application to negative-working photoresists

      Masahiro Furutani, Hiroshi Kobayashi, Takahiro Gunji, Yoshimoto Abe and Koji Arimitsu

      Article first published online: 21 FEB 2015 | DOI: 10.1002/pola.27551

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      Functional silicone resins bearing both base-amplifying units and photobase-generating units to suppress excess diffusion of base species were designed. These resins are decomposed autocatalytically after UV irradiation and subsequent heating, which indicates progression of base-proliferation reactions. High photosensitivity is accomplished, and the sensitivity of the base-proliferation reaction system is about 490 times better than that of the corresponding base-catalytic reaction system. A 4 × 10 µm line-and-space pattern has also been fabricated.

    12. Amphiphilic pentablock copolymers and their blends with PDMS for antibiofouling coatings

      Elisa Martinelli, Elisa Guazzelli, Cristina Bartoli, Matteo Gazzarri, Federica Chiellini, Giancarlo Galli, Maureen E. Callow, James A. Callow, John A. Finlay and Sophie Hill

      Article first published online: 21 FEB 2015 | DOI: 10.1002/pola.27554

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      Novel amphiphilic ABCBA pentablock copolymers were synthesized via ATRP. The presence of a central siloxane block allowed for dispersion of the copolymers in a crosslinked PDMS matrix in various loadings. Inclusion of the copolymer in the PDMS-matrix coatings enhanced the HSA and calf serum protein adsorption and decreased the adhesion strength of the sporelings of fouling macroalga Ulva linza. Biological results point to a potential of these systems as fouling release coatings.

    13. pH and glucose dually responsive injectable hydrogel prepared by in situ crosslinking of phenylboronic modified chitosan and oxidized dextran

      Juan Li, Weiqiong Hu, Yajuan Zhang, Hui Tan, Xiaojun Yan, Lingling Zhao and Hongze Liang

      Article first published online: 21 FEB 2015 | DOI: 10.1002/pola.27556

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      pH and glucose dually responsive injectable hydrogels are synthesized based on biocompatible phenylboronic modified chitosan and oxide dextran, through the formation of a dynamic covalent imine bond and phenylboronate ester. Drugs and cells can be encapsulated inside the hydrogels through the in situ gel-forming process. Sustained and controlled drug release, and sensitive cell proliferation in the 3D hydrogel matrix are observed, showing potential applications of the system in biomedicine.

    14. Synthesis and polymerization of phenylacetylene having two carbazole units and properties of the formed polymer

      Natsuhiro Sano, Kazuki Banzai, Shigeki Naka, Hiroyuki Okada and Fumio Sanda

      Article first published online: 21 FEB 2015 | DOI: 10.1002/pola.27557

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      Novel carbazole-containing acetylene monomer 1 was synthesized, polymerized and copolymerized with phenylacetylene (PA). Polymers with number-average molecular weights ranging from 7800 to 33,200 were obtained in 60%–quantitative yields. The absorption band edge of poly(1-co-PA) (1PA = 8:2) was positioned at a wavelength longer than those of 1 and polyvinylcarbazole. The copolymer emitted fluorescence with 60% quantum yield, and worked as a hole transport material of an OLED.

  10. Rapid Communication

    1. Crosslinking of fluoroelastomers by “click” azide–nitrile cycloaddition

      Guillaume Tillet, Gérald Lopez, Ming-Hong Hung and Bruno Améduri

      Article first published online: 7 FEB 2015 | DOI: 10.1002/pola.27549

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      A fluoroelastomer that bears pendant nitrile groups is crosslinked with a telechelic bis-azido fluorinated curing agent by “click” azide–nitrile cycloaddition. Thermogravimetric analyses of the resulting press cured films reveal an improvement by 20 °C of the thermal degradation profile under air, compared to that of the corresponding uncured fluoroelastomer.

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