Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 53 Issue 20

15 October 2015

Volume 53, Issue 20

Pages i–ii, 2313–2430

  1. Cover Image

    1. Top of page
    2. Cover Image
    3. Rapid Communications
    4. Articles
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      Cover Image, Volume 53, Issue 20 (pages i–ii)

      Article first published online: 2 SEP 2015 | DOI: 10.1002/pola.27802

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      On page 2320 (DOI: 10.1002/pola.27758), Jiawen Zhang, Lingmin Yi, Kai Xu, Jing Li, and Dongzhi Lai report a new approach for producing fluorescent gold nanoparticles (AuNPs) using poly(ethylene oxide) (PEO) homopolymers as the reductants in the micelles of amphiphilic poly[methyl(3,3,3-trifluoropropyl)siloxane]-b-poly(acrylic acid) (PMTFPS-b-PAA) block copolymers. In the block copolymer micelles, metal ions along with PEO chains would accumulate nearby the carboxylic groups in PAA blocks due to the interaction between metal ions and carboxylic groups. And then, metal ions were reduced by PEO homopolymers and spherical AuNPs were rapidly formed thereafter.

  2. Rapid Communications

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    3. Rapid Communications
    4. Articles
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      Combined atom-transfer radical polymerization and ring-opening polymerization to design polymer–polypeptide copolymer conjugates toward self-aggregated hybrid micro/nanospheres for dye encapsulation (pages 2313–2319)

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

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

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

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      New approach for producing fluorescent gold nanoparticles: Poly(ethylene oxide) homopolymers as reductants in the micelles of amphiphilic fluorosilicone-containing block copolymers (pages 2320–2325)

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

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

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

  3. Articles

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    2. Cover Image
    3. Rapid Communications
    4. Articles
    1. Spotlight Article

      Soft Matter Nanoparticles with Reactive Coronal Pentafluorophenyl Methacrylate Residues via Non-Polar RAFT Dispersion Polymerization and Polymerization-Induced Self-Assembly (pages 2326–2335)

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

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

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

    2. Preparation of microporous polymers in the form of particles and a thin film from hyperbranched polyphenylenes (pages 2336–2342)

      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.

    3. Synthesis of hyperbranched polyacetals via an + b2-type polyaddition (n = 3, 8, 18, and 21): Candidate resists for extreme ultraviolet lithography (pages 2343–2350)

      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.

    4. RAFT polymerization in supercritical carbon dioxide based on an induced precipitation approach: Synthesis of 2-ethoxyethyl methacrylate/acrylamide block copolymers (pages 2351–2356)

      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.

    5. Spotlight Article

      Norbornene derivatives from a metal-free, strain-promoted cycloaddition reaction: New building blocks for ring-opening metathesis polymerization reactions (pages 2357–2362)

      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.

    6. Synthesis and characterization of benzimidazolium-functionalized polysulfones as anion-exchange membranes (pages 2363–2373)

      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.

    7. Reduction-cleavable hyperbranched polymers with limited intramolecular cyclization via click chemistry (pages 2374–2380)

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

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

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

    8. Postfunctionalization of polyoxanorbornene backbone through the combination of bromination and nitroxide radical coupling reactions (pages 2381–2389)

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

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

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

    9. A New D–A conjugated polymer P(PTQD-BDT) with PTQD acceptor and BDT donor units for BHJ polymer solar cells application (pages 2390–2398)

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

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

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

    10. Synthesis and crosslinking of hyperbranched poly(n-nonyl acrylate) to form organogels (pages 2399–2410)

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

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

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

    11. Radical Polymerization of methacrylates with an adamantane-like rigid core derived from naturally occurring myo-inositol (pages 2411–2420)

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

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

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

    12. Spotlight Article

      Oxime functionalization strategy for iodinated poly(epsilon-caprolactone) X-ray opaque materials (pages 2421–2430)

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

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

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