Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 52 Issue 19

1 October 2014

Volume 52, Issue 19

Pages i–iv, 2715–2860

  1. Cover Image

    1. Top of page
    2. Cover Image
    3. Articles
    4. Erratum
    1. You have free access to this content
      Cover Image, Volume 52, Issue 19 (pages i–ii)

      Article first published online: 26 AUG 2014 | DOI: 10.1002/pola.27368

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      A random copolymer [p(MMA/DMAB)] composed of methyl methacrylate (MMA) and 2,2-dimethoxy-1,2-di(4-methacryloyloxy)phenylethane-1-one (DMAB), which can simultaneously act as a photo-radical initiator and cross-linkable monomer, is prepared by free radical random copolymerization. On page 2822 (DOI: 10.1002/pola.27308), Ryusuke Enomoto, Masanao Sato, Shota Fujii, Tomoyasu Hirai, Atsushi Takahara, Kazuhiko Ishihara, and Shin-ichi Yusa report that hydrophilic 2-methacryloyloxyethyl phosphorylcholine (MPC) is graft-copolymerized from the hydrophobic p(MMA/DMAB) film in water by photo-cleavage of the DMAB unit. MPC can be selectively grafted onto the surface of the film only at UV-irradiated sites. The p(MMA/DMAB) film has potential photolithographic and biomedical applications since the film surface properties are controllable using various vinyl monomers selectively on UV-irradiated sites.

    2. You have free access to this content
      Cover Image, Volume 52, Issue 19 (pages iii–iv)

      Article first published online: 26 AUG 2014 | DOI: 10.1002/pola.27369

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      On page 2715 (DOI: 10.1002/pola.27288), Jizhen Zhang, Aihua Li, Huihui Liu, Dongjiang Yang, and Jingquan Liu report the successful application of a novel photochemical photoinitiator based on phenylmethoxy-modified Nb(OH)5 to RAFT controlled polymerizations under visible light irradiation at ambient temperature. A very short induction period is observed along with good control over the polymerizations up to high conversions. This allows the polymerizations to be controlled at will with on/off illumination. This facile, convenient, and inexpensive photoinitiated polymerization can be used as an alternative to traditional thermal or photo-based free radical polymerizations and may lead to extensive applications in the future.

  2. Articles

    1. Top of page
    2. Cover Image
    3. Articles
    4. Erratum
    1. Well-controlled RAFT polymerization initiated by recyclable surface-modified Nb(OH)5 nanoparticles under visible light irradiation (pages 2715–2724)

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

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

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

    2. Synthesis and self-assembly of thermosensitive double-hydrophilic poly(N-vinylcaprolactam)-b-poly(N-vinyl-2-pyrrolidone) diblock copolymers (pages 2725–2737)

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

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

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

    3. Spotlight Article

      Selective interactions of a high-molecular-weight polycarbazole with different commercial nanotube samples (pages 2738–2747)

      Nicole A. Rice and Alex Adronov

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

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

    4. Siloxane-mediated ethylene oligomerization with iron-based catalysts: Retarding the polymer formation (pages 2748–2759)

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

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

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

    5. A novel solventless coating method to graft low-molecular weight polyethyleneimine on silica fine powders (pages 2760–2768)

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

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

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

    6. Spotlight Article

      Poling and crosslinking processes in NLO polymers (pages 2769–2775)

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

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

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

    7. Advances in the frontal ring opening metathesis polymerization of dicyclopentadiene (pages 2776–2780)

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

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

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

    8. High-performance segmented polyurea by transesterification of diphenyl carbonates with aliphatic diamines (pages 2781–2790)

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

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

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

    9. A combining signal amplification of atom transfer radical polymerization and redox polymerization for visual biomolecules detection (pages 2791–2799)

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

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

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      Ce4+ as an oxidant in redox polymerization directly combined with the hydroxyl groups generated from atom transfer radical polymerization allows for signal amplification in the visualization of biomolecules.

    10. Synthesis of brush-shaped polymers consisting of a poly(phenylacetylene) backbone and pendant poly(vinyl ether)s via selective reaction of 2-Vinyloxyethyl 4-Ethynylbenzoate (pages 2800–2805)

      Jin Motoyanagi, Kiriko Higashi and Masahiko Minoda

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

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

    11. Anionic alternating copolymerization of α-arylacrylates with methyl methacrylate: Effect of monomer sequence on fluorescence (pages 2806–2814)

      Yasuhiro Kohsaka, Eiji Yamaguchi and Tatsuki Kitayama

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

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

    12. Synthesis and photoluminescence behaviors of anthracene-layered polymers (pages 2815–2821)

      Yasuhiro Morisaki, Tatsuya Nakano and Yoshiki Chujo

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

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

    13. Surface patterned graft copolymerization of hydrophilic monomers onto hydrophobic polymer film upon UV irradiation (pages 2822–2829)

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

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

      Thumbnail image of graphical abstract

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

    14. Control of microstructure and gradient property of polymer network by photopolymerizable silicone-containing nanogel (pages 2830–2840)

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

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

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

    15. Spotlight Article

      Postpolymerization modification of reactive polymers derived from vinylcyclopropane. III. Polymer sequential functionalization using a combination of amines with alkoxyamines, hydrazides, isocyanates, or acyl halides (pages 2841–2849)

      Denis Hervé Seuyep Ntoukam, Gerrit Albert Luinstra and Patrick Theato

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

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

    16. Hydroxyfunctional oxetane-inimers with varied polarity for the synthesis of hyperbranched polyether polyols via cationic ROP (pages 2850–2859)

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

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

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

  3. Erratum

    1. Top of page
    2. Cover Image
    3. Articles
    4. Erratum
    1. You have free access to this content
      Erratum: Effects of the structure and morphology of zinc glutarate on the fixation of carbon dioxide into polymer (page 2860)

      Y. Z. Meng, L. C. Du, S. C. Tjong, Q. Zhu and Allan S. Hay

      Article first published online: 26 AUG 2014 | DOI: 10.1002/pola.27374

      This article corrects:

      Effects of the structure and morphology of zinc glutarate on the fixation of carbon dioxide into polymer

      Vol. 40, Issue 21, 3579–3591, Article first published online: 13 SEP 2002

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