Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 53 Issue 13

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. Rapid Communications

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      Biological evaluation of 1,2,3-triazole-based polymers for potential applications as hard tissue material

      David Pretzel, Benedict Sandmann, Matthias Hartlieb, Jürgen Vitz, Stefan Hölzer, Nicole Fritz, Norbert Moszner and Ulrich S. Schubert

      Article first published online: 25 MAY 2015 | DOI: 10.1002/pola.27676

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      This contribution deals with the synthesis and subsequent bulk polymerization of multifunctional electron-deficient internal alkynes with several multifunctional azides in a metal-free 1,3-dipolar azide–alkyne cycloaddition. The biocompatibility of alkynes, azides, and resulting networks was investigated in a cell biological study. All monomers revealed distinctive concentration-dependent cytotoxic properties. These harmful side effects on the cell integrity were completely diminished after polymerization of the educts resulting in materials with highly biocompatible properties.

  2. Articles

    1. Functionalized PEG-b-PAGE-b-PLGA triblock terpolymers as materials for nanoparticle preparation

      Justyna A. Czaplewska, Tobias C. Majdanski, Markus J. Barthel, Michael Gottschaldt and Ulrich S. Schubert

      Article first published online: 22 MAY 2015 | DOI: 10.1002/pola.27674

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      The poly(ethylene glycol)-block-poly(allyl glycidyl ether) as well as their copolymers with poly(lactide-co-glycolide) are prepared by introduction of a primary OH group and subsequent ring-opening polymerization. The polymers are further functionalized via thiol-ene reaction. Spherical particles with diameters around 200 nm and a relatively low PDIparticle value of 0.03–0.1 could be obtained from the functional amphiphilic block copolymers (DLS and SEM). The obtained nanoparticles represent promising candidates for drug delivery studies.

    2. Ru(II)(tpy)2-functionalized hydrogels: Synthesis, reversible responsiveness, and coupling with the belousov-zhabotinsky reaction

      Hongwei Zhou, Yan Yang, Guohe Xu, Weixing Chen, Wenzhi Zhang, Qiguan Wang, Zhaohui Zheng and Xiaobin Ding

      Article first published online: 21 MAY 2015 | DOI: 10.1002/pola.27690

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      Ru(II)(Tpy)2-functionalized hydrogels are designed and prepared, the reversible redox responsiveness of the synthetic hydrogels is investigated, the occurrence of the BZ reaction in the hydrogel networks is demonstrated, and the self-oscillating properties of the BZ reaction are studied.

    3. 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.

    4. Novel chiral PEDOTs for selective recognition of 3,4-dihydroxyphenylalanine enantiomers: Synthesis and characterization

      Liqi Dong, Baoyang Lu, Xuemin Duan, Jingkun Xu, Dufen Hu, Kaixin Zhang, Xiaofei Zhu, Hui Sun, Shouli Ming, Zhipeng Wang and Shijie Zhen

      Article first published online: 21 MAY 2015 | DOI: 10.1002/pola.27695

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      This article reports two novel compounds of side-chain functionalized 3,4-ethylenedioxythiophenes (EDOTs), that is, (2R)-(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methyl 2-phenylpropanoate ((R)-EDTM-PP) and (2S)-(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methyl 2-phenylpropanoate ((S)-EDTM-PP). The new compounds can be employed as chiral electrodes to successfully recognize 3,4-dihydroxyphenylalanine (DOPA) enantiomers.

    5. 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.

    6. Boron subphthalocyanine polymers: Avoiding the small molecule side product and exploring their use in organic light-emitting diodes

      Benoît H. Lessard, Kathleen L. Sampson, Trevor Plint and Timothy P. Bender

      Article first published online: 19 MAY 2015 | DOI: 10.1002/pola.27685

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      The synthesis of boron subphthalocyanine (BsubPc)-containing polymers, while circumventing the formation of a known side-product, is described. The resulting BsubPc polymers are characterized by electrochemistry, photoluminescence spectroscopy, and even used as an active component in preliminary polymer-based organic light-emitting diodes. These polymer characterizations and device integration represent a first for BsubPc polymers.

    7. 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.

  3. Rapid Communication

    1. Facile synthesis of formaldehyde-based polyether(-carbonate) polyols

      Jens Langanke, Jörg Hofmann, Christoph Gürtler and Aurel Wolf

      Article first published online: 19 MAY 2015 | DOI: 10.1002/pola.27687

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      Paraformaldehyde (pFA) was utilized as abundant building block to synthesize liquid and remarkably stable pFA-poly(alkoxy) and pFA-poly(alkoxy)(carbonate) triblock polyols by graft oligomerization of epoxides and variable amounts of CO2. The resulting tailor-made oligo diols are highly interesting precursors: They are partially made from alternative feedstock and are well suited as starting material for state-of-the-art polyurethane chemistry. Moreover, this study demonstrates the general feasibility of a novel polyether polyol process with a significantly reduced epoxide demand.

    2. Facile synthesis of fluorene-based π-conjugated polymers via sequential bromination/direct arylation polycondensation

      Hitoshi Saito, Junpei Kuwabara and Takaki Kanbara

      Article first published online: 19 MAY 2015 | DOI: 10.1002/pola.27689

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      The synthesis of fluorene-based π-conjugated polymers via sequential bromination and Pd-catalyzed direct arylation polycondensation was demonstrated; the protocol allows dual functionalization of each aromatic monomer in one-pot fashion. This synthetic protocol afforded the corresponding polymers with high molecular weights in good yields (up to yield 80%, Mn 34,500).

  4. Articles

    1. Synthesis of polycarbosilanes having sugar-derived structures as novel materials for cell cultivation

      Kozo Matsumoto, Takanori Fujiwara, Mitsuaki Goto and Takeshi Endo

      Article first published online: 19 MAY 2015 | DOI: 10.1002/pola.27682

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      Polycarbosilanes having glucose or glucosamine-derived structures in the polymer side chains were synthesized via ene-thiol reaction of polycarbosilane having C=C double bonds with thiol-modified glucose or thiol-modified glucosamine. Their application to materials for cell cultivation was investigated.

    2. Redox initiated cationic polymerization of oxetanes

      James V. Crivello

      Article first published online: 14 MAY 2015 | DOI: 10.1002/pola.27553

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      3,3-Disubstituted oxetane monomers undergo rapid, exothermic redox initiated cationic ring-opening polymerization in the presence of a diaryliodonium or triarylsulfonium salt oxidizing agent and a hydrohydrosilane reducing agent. The palladium complex, Cl2(COD)PdII, was used as a catalyst for this reaction.

    3. 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.

    4. Synthesis of pyrene-capped polystyrene by free radical polymerization and its application in direct exfoliation of graphite into graphene nanosheets

      Haining Wang, Zhao Chen, Lanxia Xin, Jian Cui, Shuai Zhao and Yehai Yan

      Article first published online: 7 MAY 2015 | DOI: 10.1002/pola.27675

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      By use of a particularly designed azo-based pyrenyl compound as the initiator, free radical polymerization was demonstrated to be a feasible technique for synthesis of single pyrene group end-capped polystyrene, which could be applied as an efficient dispersant in direct exfoliation of graphite into graphene nanosheets.

    5. Oxetane-terminated telechelic epoxy-functional polyesters as cationically polymerizable thermoset resins: Tuning the reactivity with structural design

      Susana Torron and Mats Johansson

      Article first published online: 7 MAY 2015 | DOI: 10.1002/pola.27673

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      Telechelic oligomers containing oxetane end groups and epoxides in the main chain have been prepared through enzyme catalyzed esterification of a biobased monomer. Control of the final mechanical properties of the networks is achieved by tailoring the reactivity of those groups. The formed oligomers revealed a preferred copolymerization route to build the thermosets when compared with the homopolymerizations.

    6. Synthesis and phase behavior of a polynorbornene-based molecular brush with dual “jacketing” effects

      Yangyang Qiao, Jing Ping, Haijian Tian, Qikai Zhang, Sheng Zhou, Zhihao Shen, Shijun Zheng and Xinghe Fan

      Article first published online: 6 MAY 2015 | DOI: 10.1002/pola.27646

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      A series of molecular brushes with dual “jacketing” effects were synthesized by ATRP and ROMP using the “grafting through” method. All the PNb-g-PMPCS molecular brushes form a ΦN phase. The confinement effect and the increased MW effect of the brush architecture play important roles in the phase behaviors of these molecular brushes.

    7. Consideration on formation mechanism of aromatic polyamide hollow spheres prepared by reaction-Induced phase separation

      Hirofumi Nakayama, Yuji Fujitsu, Tetsuya Uchida, Shinichi Yamazaki and Kunio Kimura

      Article first published online: 6 MAY 2015 | DOI: 10.1002/pola.27683

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      Formation mechanism of poly(1,4-phenylene-5-hydroxyisophthalamide) hollow spheres prepared by the reaction-induced phase separation during polymerization was considered from the view points of eliminated small molecules, polymer structure, and cross-linking reaction. Water was the most desirable to form gas-bubbles and rigid polymer structure was also needed for the rapid solidification of droplets. Further, the formation of the cross-linked skin layer was important to encapsulate gas-bubbles in the droplets.

    8. Fabrication and characterization of UV-crosslinkable thermoresponsive composite fibers with magnetic properties

      Shih-Ru Huang, King-Fu Lin, Trong-Ming Don, Wen-Yen Chiu and Mei-Fei Lin

      Article first published online: 6 MAY 2015 | DOI: 10.1002/pola.27684

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      Stimuli-responsive materials recently received much attention due to their unique sensitivities and functionalities. In order to manufacture functional drug carrier with higher drug loading, electrospinning technique was used to fabricate fibrous composite with thermoresponsivity and magnetic properties. Drug release behavior of magnetic thermoresponsive composite (MTC) drug carrier was studied in the article. It has potential in controlled drug release system.

    9. RAFT of sulfobetaine for modifying poly(glycidyl methacrylate) microspheres to reduce nonspecific protein adsorption

      Jana Koubková, Hana Macková, Vladimír Proks, Miroslava Trchová, Jiří Brus and Daniel Horák

      Article first published online: 30 APR 2015 | DOI: 10.1002/pola.27681

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      Monodisperse poly(glycidyl methacrylate) microspheres were grafted with zwitterionicpoly{[3-(methacryloylamino)propyl]dimethyl(3-sulfopropyl)ammonimum hydroxide} using RAFT polymerization initiated from the particle surface. Increasing amounts of polysulfobetaine on the surface rendered the microspheres hydrophilic and biocompatible and significantly reduced nonspecific adsorption of bovine serum albumin.

    10. Bioreducible hyperbranched polyglycerols with disulfide linkages: Synthesis and biocompatibility evaluation

      Rajesh A. Shenoi, Irina Chafeeva, Benjamin F. L. Lai, Sonja Horte and Jayachandran N. Kizhakkedathu

      Article first published online: 29 APR 2015 | DOI: 10.1002/pola.27672

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      Anionic ring opening polymerization of glycidol and a disulfide-containing epoxide monomer was used for the synthesis of multifunctional and water-soluble disulfide-bearing biodegradable hyperbranched polyglycerols both in the low and high molecular weight range. The polymers were degraded to lower molecular weight polymer fragments in presence of reducing agents such as TCEP, DTT, and glutathione. The polymers also showed excellent biocompatibility profiles even at very high concentrations and could be useful as nanocarriers for intracellular delivery of therapeutics.

    11. Shape memory biomaterials prepared from polyurethane/ureas containing sulfated glucose

      Qinyuan Chai, Yongshun Huang and Neil Ayres

      Article first published online: 29 APR 2015 | DOI: 10.1002/pola.27668

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      Crosslinked polymers were synthesized using monomers modified with glucose. The polymers showed shape memory behavior. A glass transition temperature of 39 °C, close to physiological temperatures, was obtained. The polymer recovered to the permanent shape when heated to 50 °C. The surface of a film of the polymer can be sulfated to achieve increased blood-compatibility without sacrificing the shape memory properties.

    12. 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.

  5. Rapid Communication

    1. Facile and versatile platform for the preparation of functional polyethylenes via thiol-ene chemistry

      Zeyun Xiao, Christopher W. Bennett and Luke A. Connal

      Article first published online: 27 APR 2015 | DOI: 10.1002/pola.27667

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      A modular approach to the preparation of functional polyethylenes is presented. Polycyclooctene polymers are prepared via ring opening metathesis polymerization. The internal alkene bonds of the subsequent polyclycooctenes are exploited using photochemical thiol–ene click chemistry. A range of branched, amphiphilic, and fluorinated polyethylenes are synthesized.

  6. Articles

    1. Synthesis of partially fluorinated poly(arylene ether sulfone) multiblock copolymers bearing perfluorosulfonic functions

      Luca Assumma, Cristina Iojoiu, Régis Mercier, Sandrine Lyonnard, Huu Dat Nguyen and Emilie Planes

      Article first published online: 23 APR 2015 | DOI: 10.1002/pola.27650

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      The partially fluorinated poly(arylene ether sulfone) multiblock copolymers with well controlled block lengths and high molecular weight were successfully synthesized by “one pot two reactions synthesis.” The Ionomers bearing perfluoro alkyl sulfonic acids, obtained by regioselective modification of multiblock copolymers, lead to highly nanostructured membranes with morphology and conductivity close to those of Nafion.

    2. Antibacterial poly(ethylene terephthalate) surfaces obtained from thymyl methacrylate polymerization

      Sophie Bedel, Bénédicte Lepoittevin, Ludovic Costa, Olivier Leroy, Diana Dragoe, Jérôme Bruzaud, Jean-Marie Herry, Morgan Guilbaud, Marie-Noëlle Bellon-Fontaine and Philippe Roger

      Article first published online: 23 APR 2015 | DOI: 10.1002/pola.27647

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      A method for fabrication of poly(thymyl methacrylate) brushes grafted on poly(ethylene terephthalate) films is described. The monomer is obtained from thymol essential oil. The modified surfaces are prepared by “grafting from” using atom transfer radical polymerization and present antibacterial properties against different bacteria strains.

    3. Oligomeric aliphatic–aromatic ether containing phthalonitrile resins

      Matthew Laskoski, Arianna Neal, Mollie B. Schear, Teddy M. Keller, Holly L. Ricks-Laskoski and Andrew P. Saab

      Article first published online: 23 APR 2015 | DOI: 10.1002/pola.27659

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      A series of aliphatic containing phthalonitrile resins have been synthesized and characterized. The cured polymer shows good physical properties and low water absorption.

    4. Energy transfer through heterogeneous dyes-substituted fluorene-containing alternating copolymers and their dual-emission properties in the films

      Hyeonuk Yeo, Kazuo Tanaka and Yoshiki Chujo

      Article first published online: 23 APR 2015 | DOI: 10.1002/pola.27652

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      A series of the alternating fluorene copolymers modified with pyrene or 9,10-diphenylanthracene and BODIPY at the cardo carbon based on the red-emissive donor-acceptor structure were prepared. From the measurements of the optical properties, the energy transfer efficiencies were evaluated. In summary, variable energy transfer efficiencies were observed between the side chains and from the side chain to the main chain. Finally, the dual-emissive polymers were obtained in the film states.

    5. Synthesis and characterization of chiral poly(alkyl isocyanates) by coordination polymerization using a chiral half-titanocene complex

      Ioannis Choinopoulos, Spyros Koinis and Marinos Pitsikalis

      Article first published online: 23 APR 2015 | DOI: 10.1002/pola.27669

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      Chiral polymers are used in high technology applications. The chirality of polyisocyanates derives from their helical structure. The chiral 2-(S)-butoxy group of the novel half-titanocene complex [CpTiCl2(O-(S)−2-Bu)] is responsible for the production of the left-handed poly(alkyl isocyanate) helices exclucively. The polymerization reaction is well controlled and proceeds in a chiral manner. The polymers maintain their structure in a wide range of temperatures. Cyclotrimerization, instead of polymerization is favored for the sterically hindered monomers.

    6. Synthesis and structure–property relationship of carbazole-alt-benzothiadiazole copolymers

      Jules Oriou, Feifei Ng, Georges Hadziioannou, Cyril Brochon and Eric Cloutet

      Article first published online: 18 APR 2015 | DOI: 10.1002/pola.27660

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      Four π-conjugated copolymers based on carbazole and benzothiadiazole (PCBT) were prepared by Suzuki cross-coupling reaction. Their structures differed by linkage position and geometry of the solubilizing chain on the carbazole subunits. These organic materials were characterized and showed promising properties for organic electronics applications. The differences in structure were shown to influence the optical properties.

    7. Hyperbranched polytriazine grafted reduced graphene oxide and its application

      Chao Liu, Hongxia Yan, Lingxia Yuan, Zhengyan Chen and Mengmeng Zhang

      Article first published online: 18 APR 2015 | DOI: 10.1002/pola.27661

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      Hyperbranched polytriazineis used to modify reduced graphene oxide, making it amphipathic and improving its distribution in polymer composites. In turn, this greatly improves the thermal stability and electrical conductivity of its polymer composites as compared with unmodified graphene oxide composites.

    8. Understanding of nanogels swelling behavior through a deep insight into their morphology

      Aintzane Pikabea, Garbiñe Aguirre, Jose I. Miranda, Jose Ramos and Jacqueline Forcada

      Article first published online: 18 APR 2015 | DOI: 10.1002/pola.27653

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      The morphology and swelling behavior of biocompatible and dual-stimuli-responsive nanogels crosslinked with different crosslinkers were analyzed and related by combining the Flory–Rehner theory with 1H-NMR and PCS data.

    9. A benign initiating system for cationic polymerization of isobutyl vinyl ether: Silver salt/aryl(alkyl) halide/lewis base

      Li Lin, Guangyou Zhang, Koichi Kodama, Mikio Yasutake and Takuji Hirose

      Article first published online: 18 APR 2015 | DOI: 10.1002/pola.27656

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      Aryl(alkyl) halides and silver salts were studied as an ecofriendly initiating system for cationic polymerization of isobutyl vinyl ether (IBVE). Me2S was shown to be an effective Lewis base (LB) for controlling the reaction. Detailed study of various benzyl cations and the order of reagent addition showed that the reaction was controlled by the steric and electronic features of the benzyl halides, LBs, and IBVE. A plausible reaction mechanism was proposed.

    10. A new route to atactic polypropylene: The second life of premetallocene homogeneous polymerization catalyst

      Yury V. Kissin, Laura A. Rishina, Svetlana S. Lalayan and Vadim G. Krasheninnikov

      Article first published online: 17 APR 2015 | DOI: 10.1002/pola.27651

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      Ternary Ti(Oiso-Pr)4 - AlEt2Cl/MgBu2 catalyst polymerizes propylene at 30–50 °С to a predominantly amorphous atactic polymer. The 13C NMR spectrum of the heptane-soluble fraction of the polymer consists of signals of various stereo-irregular pentads and heptads; its [mmmm] = 0.21.

  7. Rapid Communication

    1. Correlation between Polydispersities of Molecular Weight Distribution and Particle Size Distribution in RAFT Emulsion Polymerization of Styrene

      Kun Yan, Xiang Gao and Yingwu Luo

      Article first published online: 15 APR 2015 | DOI: 10.1002/pola.27654

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      The polydispersities of molecular weight distribution and particle size distribution are found to be strongly correlated with each other and to be dramatically increased as the initiator concentrations are reduced in the RAFT emulsion polymerizations. The mechanism underlying this is the particle activation/deactivation process between particles with and without a radical—similar to reactions between propagating radicals and polymeric dormant chains in homogeneous RAFT polymerization.

  8. Articles

    1. From single-chain folding to polymer nanoparticles via intramolecular quadruple hydrogen-bonding interaction

      Fei Wang, Hongting Pu, Ming Jin, Haiyan Pan, Zhihong Chang, Decheng Wan and Jiang Du

      Article first published online: 15 APR 2015 | DOI: 10.1002/pola.27657

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      The single-chain folding of P(MMA-co-EMA-DeAP) and the formation of the nanoparticles in diluted solution are achieved via supramolecular interaction and intramolecular collapsing during the disruption-reformation process of hydrogen bonding triggered by water.

    2. Lysine-based functional blocked isocyanates for the preparation of polyurethanes provided with pendant side groups

      Jie Yin, Jur Wildeman and Ton Loontjens

      Article first published online: 15 APR 2015 | DOI: 10.1002/pola.27658

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      A general methodology was found to prepare linear polyurethanes, decorated with pendant (bio)functional side groups by using (bio)functionalized blocked diisocyanates and polyols. The functionalizable blocked isocyanate precursor, caprolactam blocked lysine diisocyanate methyl ester, was prepared in high yields by reacting the methyl ester of lysine with carbonyl biscaprolactam.

  9. Erratum

    1. You have free access to this content
      Erratum: Exploring the synthesis and impact of end-functional poly(3-hexylthiophene)

      Nisha V. Handa, Abigail V. Serrano, Maxwell J. Robb and Craig J. Hawker

      Article first published online: 15 APR 2015 | DOI: 10.1002/pola.27666

      This article corrects:

      Exploring the synthesis and impact of end-functional poly(3-hexylthiophene)

      Vol. 53, Issue 7, 831–841, Article first published online: 7 FEB 2015

  10. Articles

    1. Synthesis of amphiphilic polymer networks with guest-host properties

      Mathis Hodge, Gaumani Gyanwali, Cameron Villines and Jeffery L. White

      Article first published online: 13 APR 2015 | DOI: 10.1002/pola.27637

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      Amphiphilic polymer crosslinked networks with specific lengths linking cyclodextrin (CD) nodes synthesized modularly are presented. Linker type and length variation bring about hydrophilic/hydrophobic tuning of the network. Guest-host capability is adjusted by the size variation of α-, β-, and γ-CDs. Ethylene glycol and polyethylene oxide linkers result in insoluble networks that swell to varying degrees in polar protic, polar aprotic, and chlorinated solvents such as water, methanol, ethanol, dimethylsulfoxide, dimethylformamide, methylene chloride, and chloroform.

    2. Structure/reactivity/photoinitiation ability relationships in novel benzo pyrazolo (or imidazo) isoquinolinone derivatives upon visible light LEDs

      Pu Xiao, Frédéric Dumur, Jing Zhang, Mariem Bouzrati-Zerelli, Bernadette Graff, Didier Gigmes, Jean Pierre Fouassier and Jacques Lalevée

      Article first published online: 13 APR 2015 | DOI: 10.1002/pola.27640

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      The types (nitro- or amino- functional group) and numbers (one or two) of substituent on the isoquinolinone derivatives (IQNs) play significant roles in both their photochemical properties and their photoinitiation ability for photopolymerization upon exposure to the different LEDs. For instance, some initiating systems-based on IQNs exhibit very high efficiency for cationic photopolymerization of epoxides and free radical photopolymerization of acrylates upon exposure to the different LEDs.

    3. Silylium dual catalysis in living polymerization of methacrylates via In situ hydrosilylation of monomer

      Tieqi Xu and Eugene Y.-X. Chen

      Article first published online: 13 APR 2015 | DOI: 10.1002/pola.27641

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      Silylium ions catalyze both 1,4-hydrosilylation of monomer with R3SiH to generate the silyl ketene acetal initiator in situ and subsequent living polymerization of methacrylates.

    4. Modulation of optical and electronic properties of quinoxailine-based conjugated polymers for organic photovoltaic cells

      Ji-Hoon Kim, Chang Eun Song, Won Suk Shin, BongSoo Kim, In-Nam Kang and Do-Hoon Hwang

      Article first published online: 13 APR 2015 | DOI: 10.1002/pola.27642

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      Four donor-acceptor-type semiconducting copolymers are synthesized for use in organic photovoltaic cells. Quinoxaline (QX) or difluorinated quinoxaline (DFQX) derivatives serve as electron-accepting units, while thiophene (T) or selenophene (Se) serve as electron-donating units. Thermal stability, optical and electrochemical properties, field-effect carrier mobilities, film crystallinities, and photovoltaic performances of the polymers are investigated. Organic photovoltaic cells fabricated using the polymer composed of difluorinated QX and selenophene (PSe-DFQX) exhibited a power conversion efficiency of 5.14%.

    5. Polyaniline copolymers with solvent-mimic side chains

      Seung-Chul Lee, Chan-Keun Jung, Hoon-Joo Jung, Suck-Hyun Lee and O-Pil Kwon

      Article first published online: 11 APR 2015 | DOI: 10.1002/pola.27648

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      New polyaniline copolymers with solvent-mimic side chains for enhanced processability in various solvents were investigated. The solvent-mimic side chains, benzyloxypropyl (BOP) and dihydroxypropoxy (DHP), were introduced into copolymers and used with nonpolar aromatic and polar alcoholic solvents, respectively. Polyaniline copolymers with a small amount of side chains (<2 mol %) exhibit higher electric conductivity and better film-forming ability in nonpolar aromatic solvent than polyaniline homopolymer.

    6. Water-stable copolymers containing isocyanate moiety protected by hydrophobic styrene segment and their reaction with amines

      Ryota Seto, Kozo Matsumoto and Takeshi Endo

      Article first published online: 11 APR 2015 | DOI: 10.1002/pola.27645

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      Reactive isocyanate group was protected and stabilized by hydrophobic styrene segment and acquired high tolerance toward water. Copolymers containing isocyanate groups were synthesized by a radical copolymerization of 2-propenyl isocyanate (2PI) and styrene (St). Isocyanate groups in the copolymers were protected by hydrophobic polystyrene segments and stable on water. Protection of isocyanate group by hydrophobic styrene segment enabled water-sensitive isocyanate group to be easily handled on water.

    7. Diselenocarbamates, novel initiators in ATRP of styrene

      Feng Gao, Xiangqiang Pan, Jian Zhu, Zhengbiao Zhang, Wei Zhang and Xiulin Zhu

      Article first published online: 11 APR 2015 | DOI: 10.1002/pola.27644

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      In this article, a series of selenium-substituted carbamates were synthesized and used as mediators in atom transfer radical polymerizations. The results indicate that these diselenocarbamates can control the polymerization to some degree, as evidenced by predictable number-average molecular weights. This work provided a flexible protocol to incorporated selenium into the terminal of polystyrene, which may be useful in biotechnological and biomedical applications.

    8. Demonstration of isospecific free radical polymerization of acrylate controlled by conformation and chirality of monomer

      Hitoshi Tanaka, Yoshitaka Matsubara, Katsuhiko Kusunoki, Naoki Saito and Tatsuya Kibayashi

      Article first published online: 11 APR 2015 | DOI: 10.1002/pola.27649

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      A high isotactic heat-resistant functional polymer was prepared through a stereospecific free radical polymerization of bio-based acrylate derived from lactic acid. The work demonstrates the importance of chirality and conformation of monomer in the stereospecific polymerization, giving a clue to understanding stereochemistry in free radical polymerization and constructing a tailor-made polymer. A new approach to a sustainable synthesis of polymers in mild conditions is also established.

    9. Facile fabrication of fast recyclable and multiple self-healing epoxy materials through diels-alder adduct cross-linker

      Xiao Kuang, Guoming Liu, Xia Dong, Xianggui Liu, Jianjun Xu and Dujin Wang

      Article first published online: 11 APR 2015 | DOI: 10.1002/pola.27655

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      A reversibly cross-linked epoxy resin with efficient reprocessing and intrinsic self-healing has been prepared from a newly synthesized diamine Diels-Alder (DA) adduct cross-linker and a commercial epoxy oligomer. The methodology developed in this work takes smart and environmentally benign epoxy to the next level of simplicity and provides new insights in the modification of traditional engineering plastics as a functional material.

    10. Side chain engineering and conjugation enhancement of benzodithiophene and phenanthrenequnioxaline based conjugated polymers for photovoltaic devices

      Ying Sun, Chao Zhang, Bin Dai, Baoping Lin, Hong Yang, Xueqin Zhang, Lingxiang Guo and Yurong Liu

      Article first published online: 10 APR 2015 | DOI: 10.1002/pola.27643

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      Following the design concept of conjugation enlargement and coplanar geometry tuning, a series of conjugated polymers based on the benzodithiophene donor unit and phenanthrenequnioxaline acceptor unit with different side chains have been synthesized. The influence of side chain engineering and conjugation enhancement on the thermal, optical, electrochemical and photovoltaic properties of the polymers have been investigated and discussed in details.

    11. Synthesis and physical properties of highly branched perfluorinated polymers from AB and AB2 monomers

      Matthew J. Quast, Aaron D. Argall, Cassandra J. Hager and Anja Mueller

      Article first published online: 10 APR 2015 | DOI: 10.1002/pola.27639

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      Several highly branched copolymer systems were prepared from AB2 + AB polycondensations of perfluorinated benzyl-alcohol-bearing monomers and alkyl primary alcohol-bearing comonomers. The resulting copolymers were fully characterized. It was found that the extent of comonomer incorporation was dependent on comonomer sterics, acidity of the alcohol, and feed ratio of each monomer. In general the glass transition temperature decreased and thermal stability increased with incorporation of an AB monomer into the AB2 system.

    12. You have free access to this content
      Glassy poly(methacrylate) terpolymers with covalently attached emitters and sensitizers for low-power light upconversion

      Soo Hyon Lee, David C. Thévenaz, Christoph Weder and Yoan C. Simon

      Article first published online: 8 APR 2015 | DOI: 10.1002/pola.27626

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      A new series of light-upconverting terpolymers in which a sensitizer/emitter is reported, where the chromophore pair is covalently attached to a poly(methacrylate) backbone. A surprising relation between the composition of the polymers and the ability to upconvert green into blue light is found and explained.

    13. Marrying mussel inspired chemistry with SET-LRP: A novel strategy for surface functionalization of carbon nanotubes

      Jianwen Tian, Dazhuang Xu, Meiying Liu, Fengjie Deng, Qing Wan, Zhen Li, Ke Wang, Xiaohui He, Xiaoyong Zhang and Yen Wei

      Article first published online: 8 APR 2015 | DOI: 10.1002/pola.27638

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      A novel strategy based on a combination of mussel-inspired chemistry and SET-LRP was developed for preparation of thermoresponsive carbon nanotubes for the first time.

    14. High sensitivity sensing of nitroaromatic explosive vapors based on polytriphenylamines with AIE-active tetraphenylethylene side groups

      Wenyue Dong, Yuyu Pan, Martin Fritsch and Ullrich Scherf

      Article first published online: 3 APR 2015 | DOI: 10.1002/pola.27631

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      Two polytriphenylamines (P1 and P2) with AIE-active tetraphenylethylene side chains are synthesized. Both polymers show distinct AIE effects and a pronounced fluorescence quenching of solid state films when exposed to trinitrobenzene vapor. For P2, 63% fluorescence quenching is observed after 60 s exposure and 89% after 600 s, respectively. The fluorescence quenching response is comparable to the best performing materials from the literature. Moreover, the quenching ability shows a good reversibility.

    15. Synthesis and characterization of phenyl polysiloxane modified polyurea/polyurethanes

      Sixi Xu, Lisha Xie, Xuecheng Yu, Ying Xiong and Hongding Tang

      Article first published online: 2 APR 2015 | DOI: 10.1002/pola.27627

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      Silicone modified polyurea/urethanes with high phenyl polysiloxane contents were designed and synthesized. They exhibited obvious improved waterproof and heat resistance in comparison to pure polyurthane. An interesting void structure in the polyurea/polyurethane films was observed on the moisture induced crosslinking films.

    16. Segmented conjugated macromolecules containing silicon and boron: ADMET synthesis and luminescent properties

      Arijit Sengupta, Ami Doshi, Frieder Jäkle and Ralf M. Peetz

      Article first published online: 2 APR 2015 | DOI: 10.1002/pola.27614

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      Tri- and tetra-coordinated boron monomers were successfully polymerized to form homopolymers or random copolymers with a silicon containing co-monomer. Polymer molecular weights Mn were measured at ∼6000 to 15,000 g/mol (NMR end group analysis) with molecular weight distributions Mw/Mn ∼1.8 to 2.2. The polymers absorbed at λmax ∼317 to 406 nm and emitted at λmax ∼370 to 494 nm with fluorescent quantum efficiencies ∼24 to 48%. The copolymer with tri-coordinate boron showed highly efficient fluorescence quenching in the presence of fluoride ions at ratios boron/fluoride ∼5/1, demonstrating its potential as anion sensor.

    17. Fabrication of asymmetrically superhydrophobic cotton fabrics via mist copolymerization of 2,2,2-trifluoroethyl methacrylate

      GuangHui Xi, WanChao Fan, Lu Wang, XiangDong Liu and Takeshi Endo

      Article first published online: 2 APR 2015 | DOI: 10.1002/pola.27632

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      Asymmetrically superhydrophobic cotton fabrics were obtained via a simple method of mist copolymerization of 2,2,2-trifluoroethyl methacrylate, 2-isocyanatoethyl methacrylate, and divinylbenzene. Sufficient surface roughness was formed but the good water adsorptivity and vapor transmissibility of the original cotton fabric were inherited after the surface modification.

    18. Optically active helical polymers with pendent thiourea groups: Chiral organocatalyst for asymmetric michael addition reaction

      Haiyang Zhang, Wantai Yang and Jianping Deng

      Article first published online: 2 APR 2015 | DOI: 10.1002/pola.27630

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      Optically active helical polymers bearing pendent thiourea groups are prepared, showing remarkably asymmetric catalysis ability toward Michael reaction. The thiourea pendants and the helical polymer backbones work together in a favorable synergy effects during catalysis. Product with high yield (85%) and satisfactory ee (72%) is obtained.

    19. 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.

    20. 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.

    21. 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.

    22. 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.

    23. 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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      The siloxane-oxirane monomers are the potential solution for the polymerization shrinkage in dental composites. The network of these monomers is generated by the cationic ring opening polymerization, which starts with the initiation process of an acidic cation, which opens the oxirane ring and generates a new acidic center, a carboncation. The ring opening mechanism compensates the molecular interaction and results in decrease of volume shrinkage. This study shows a simple and effective way to synthesize and polymerize siloxane-oxirane monomers with high potential for application in dental materials.

    24. 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.

    25. 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%.

    26. 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.

  11. Rapid Communication

    1. You have free access to this content
      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.

    2. You have free access to this content
      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.

  12. Articles

    1. 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.

    2. 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.

    3. 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.

    4. 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).

    5. 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.

    6. 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.

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