Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 52 Issue 17

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

Impact Factor: 3.543

ISI Journal Citation Reports © Ranking: 2012: 12/83 (Polymer Science)

Online ISSN: 1099-0518

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

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  1. 1 - 45
  1. Rapid Communication

    1. Self-assembly and reassembly of fiber-forming dipeptides for pH-triggered DNA delivery

      Glenn R. Hafenstine, Dylan W. Domaille, Jennifer N. Cha and Andrew P. Goodwin

      Article first published online: 31 JUL 2014 | DOI: 10.1002/pola.27319

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      Hydrazone-based conjugates of PEG-dipeptide and DNA-dipeptide were designed to form stable vesicles at neutral pH, break apart at mildly acidic pH, and form large peptide fibers on release. Light scattering measurements showed that DNA-loaded vesicles of ∼80 nm were stable at pH 7.4 for 6 h and fell apart within 1 h at pH 5, with the DNA fully released from the formed fibers.

  2. Articles

    1. Synthesis and thermal, optical, and mechanical properties of sequence-controlled poly(1-adamantyl acrylate)-block-poly(n-butyl acrylate) containing polar side group

      Yoshinori Nakano, Eriko Sato and Akikazu Matsumoto

      Article first published online: 31 JUL 2014 | DOI: 10.1002/pola.27322

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      Thermal, optical, and mechanical properties of the adamantane-containing block copolymers consisting of poly(1-adamantyl acrylate) and poly(n-butyl acrylate) sequences, prepared by the sequence-controlled block copolymerization using organotellurium-mediated living radical polymerization, are described. The increases in the glass transition temperatures and activation energies due to the formation of intermolecular hydrogen bonding by the introduction of polar repeating units as well as their effects on the tensile elasticity, strength, and strain are discussed.

    2. Bulk dispersion of single-walled carbon nanotubes in silicones using diblock copolymers

      Ryan C. Chadwick, Darryl Fong, Nicole A. Rice, Michael A. Brook and Alex Adronov

      Article first published online: 30 JUL 2014 | DOI: 10.1002/pola.27313

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      Supramolecular complexes of poly(3-decylthiophene)-block-polydimethylsiloxanes (P3DT-b-PDMS) with single-walled carbon nanotubes (SWNTs) enable homogeneous incorporation of SWNTs within a bulk silicone elastomer, resulting in a low percolation threshold. The block copolymer anchors SWNTs within the silicone elastomer, allowing repeated stretching and relaxation without degradation of conductivity.

  3. Highlight

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      Functional aqueous assemblies of linear-dendron hybrids

      Greg Whitton and Elizabeth R. Gillies

      Article first published online: 30 JUL 2014 | DOI: 10.1002/pola.27316

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      Recent progress on the development of aqueous assemblies of linear-dendron hybrids capable of performing functions is described. By engineering chemical functionalities in the linear or dendritic component, as well as their architectures, a wide variety of functions—including drug encapsulation, cell targeting, lectin binding, hydrogel formation, and catalysis—can be introduced. In addition, the assemblies can be designed to respond to a variety of stimuli including pH, temperature, light, and enzymes.

  4. Articles

    1. Effects of polyethylene spacer length in polymeric electrolytes on gelation of ionic liquids and ionogel properties

      Jun'ichi Nagasawa, Sonoko Wakahara, Hajime Matsumoto, Hideyuki Kihara and Masaru Yoshida

      Article first published online: 28 JUL 2014 | DOI: 10.1002/pola.27310

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      Positively charged polyelectrolytes with N,N′ -(trans-cyclohexane-1,4-diyl)dibenzamide linkages and varying spacer lengths have been synthesized and their ability to effect gelation for six ionic liquids and the properties of the resulting ionogels have been examined. The polymers gelatinize most of the tested ionic liquids at low concentrations (0.9-50 g/L). Gel-sol transition temperatures are dependent on the spacer length, while ionic conductivities of the various ionogels are near those of the neat ionic liquids and are not affected by spacer length.

    2. Poling and crosslinking processes in NLO polymers

      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.

    3. Poly(vinylphosphonate)s functionalized polymer microspheres via rare earth metal-mediated group transfer polymerization

      Jiming Yang, Yongjiu Liang, Stephan Salzinger, Ning Zhang, Dewen Dong and Bernhard Rieger

      Article first published online: 25 JUL 2014 | DOI: 10.1002/pola.27324

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      A facile and efficient method is demonstrated for the functionalization of polymer microspheres with biocompatible poly(vinylphosphonate)s via the combination of UV-induced photopolymerization and rare-earth metal catalyzed group transfer polymerization (GTP). The surface-initiated GTP leads to a constant and remarkably rapid weight gain of the microsphere, and the accumulated tension between polymer chains induces an unprecedented fracture of the microsphere for longer polymerization time.

    4. Self-healing of poly(propylene oxide)-polybenzoxazine thermosets by photoinduced coumarine dimerization

      Baris Kiskan and Yusuf Yagci

      Article first published online: 25 JUL 2014 | DOI: 10.1002/pola.27323

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      A self-healing strategy for poly(propylene oxide)s bearing coumarine-benzoxazine units (PPO-CouBenz)s based on light induced coumarine dimerization reactions is described. The coumarine groups present in the structure undergo efficient dimerization upon irradiation at λ > 300 nm as confirmed by the UV–Vis spectral investigations. Photoinduced healing of coumarin based cured PPO-CouBenz polymer films was investigated.

  5. Rapid Communication

    1. You have free access to this content
      Kilogram scale inverse vulcanization of elemental sulfur to prepare high capacity polymer electrodes for Li-S batteries

      Jared J. Griebel, Guoxing Li, Richard S. Glass, Kookheon Char and Jeffrey Pyun

      Article first published online: 25 JUL 2014 | DOI: 10.1002/pola.27314

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      Synthetic conditions to prepare high sulfur content copolymers via inverse vulcanization on a kilogram scale is reported. By investigation of polymerization comonomer feed ratios, reaction temperature, and scale, the development of conditions to enabled the large scale synthesis of poly(sulfur-random-(1,3-diisopropenylbenzene) was conducted. We further demonstrated enhanced device performance of these sulfur copolymers as active cathode materials in Li-S batteries.

  6. Articles

    1. Synthesis of degradable molecular brushes via a combination of ring-opening polymerization and click chemistry

      Yi Shi, Xiaofeng Wang, Robert W. Graff, William A. Phillip and Haifeng Gao

      Article first published online: 23 JUL 2014 | DOI: 10.1002/pola.27307

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      Molecular brushes with an acid-degradable backbone and densely-grafted side chains (2 side chains per backbone repeating unit) are synthesized using an efficient grafting-onto method. The incorporated side chains vary from homopolymers to block copolymers and grafted polymers, and the produced molecular brushes can be degraded completely into linear polymers. When a mixture of side chains are used, the amphiphilic hetero-grafted molecular brushes can assemble in water and form either spherical micelles or hollow vesicles depending on sample compositions.

    2. Synthesis and photoluminescence behaviors of anthracene-layered polymers

      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.

    3. Postpolymerization modification of reactive polymers derived from vinylcyclopropane. III. Polymer sequential functionalization using a combination of amines with alkoxyamines, hydrazides, isocyanates, or acyl halides

      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.

    4. Anionic alternating copolymerization of α-arylacrylates with methyl methacrylate: Effect of monomer sequence on fluorescence

      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.

    5. Control of microstructure and gradient property of polymer network by photopolymerizable silicone-containing nanogel

      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.

    6. Facile synthesis of high-molecular-weight acid-labile polypeptides using urethane derivatives

      Shirley Wong and Young Jik Kwon

      Article first published online: 22 JUL 2014 | DOI: 10.1002/pola.27320

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      Preparation of acid-labile polypeptides by conventional methods, which polymerize unstable, moisture-sensitive amino acid monomers under highly restrictive conditions, has been challenging. A new method is reported that allows convenient synthesis of stable monomers and fast polymerization under easily applicable conditions, yielding high-molecular-weight acid-labile polypeptides with narrow polydispersity. The highly facile strategy demonstrated in this study could contribute to synthesizing stimuli-responsive peptide-based biomaterials for various biomedical applications.

    7. Synthetic control over the dynamics of mesoscaled cargo release from colloidal polymer vectors inside live cells

      Harvind S. Chahal, Dev S. Chahal, Patrick M. McBride and Brett A. Helms

      Article first published online: 22 JUL 2014 | DOI: 10.1002/pola.27312

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      Dynamic complementarity between colloidal polymer vectors and their electrostatically adsorbed cargo is a critical parameter that influences the rate of cargo release once inside cells. Where endogenous macromolecules within the cytosol favorably compete for adsorption sites at the vector surface, cargo can be efficiently released and trafficked to intracytosolic targets.

    8. A combining signal amplification of atom transfer radical polymerization and redox polymerization for visual biomolecules detection

      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 oxidant of redox polymerization directly combined with the hydroxyl groups generated from atom transfer radical polymerization to realize visual signal amplification.

    9. 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

      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 catalysis to afford brush-shaped polymers consisting of a polyPA backbone and pendant polyVEs.

    10. Surface patterned graft copolymerization of hydrophilic monomers onto hydrophobic polymer film upon UV irradiation

      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

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      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.

    11. High-performance segmented polyurea by transesterification of diphenyl carbonates with aliphatic diamines

      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 films made in this study has the ηinh of 0.64, tensile strength of 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.

    12. Synthesis and characterization of double hydrophilic block copolymers containing semi-rigid and flexible segments

      Alice M. Savage, Elizabeth Ullrich, Stacey M. Chin, Zachary Kiernan, Caitlyn Kost and S. Richard Turner

      Article first published online: 15 JUL 2014 | DOI: 10.1002/pola.27296

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      Two sterically crowded stilbene comonomers, 3-methyl-(E)-stilbene (3MSti) and 4-(diethylamino)-(E)-stilbene, are polymerized separately with maleic anhydride using reversible addition-fragmentation chain transfer (RAFT) polymerization techniques. RAFT agent compatibilities and reaction kinetics for each comonomer system are compared. Double hydrophilic block copolymers are synthesized from these copolymers and converted to polyelectrolytes. The isoelectric point and dissociation behavior of the polyelectrolytes are determined using ζ-potential and acid-base titrations, respectively.

    13. Siloxane-mediated ethylene oligomerization with iron-based catalysts: Retarding the polymer formation

      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 for bis(imino)pyridine iron catalysts to commercialization. An effective strategy is detailed for retarding the polymer formation by introducing siloxanes as modifiers into such systems. The influence of siloxanes could be a comprehensive result of their interactions with the catalytic components, through the modulation on both the electronic and steric effects of the active centers.

    14. A novel solventless coating method to graft low-molecular weight polyethyleneimine on silica fine powders

      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.

    15. Advances in the frontal ring opening metathesis polymerization of dicyclopentadiene

      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 catalysts to monomer and catalysts to 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.

    16. Selective interactions of a high-molecular-weight polycarbazole with different commercial nanotube samples

      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

    17. Synthesis and in vitro activity of platinum containing 2-oxazoline-based glycopolymers

      Lutz Tauhardt, David Pretzel, Stefan Bode, Justyna A. Czaplewska, Kristian Kempe, Michael Gottschaldt and Ulrich S. Schubert

      Article first published online: 9 JUL 2014 | DOI: 10.1002/pola.27290

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      Glyco(poly(2-oxazoline)s) functionalized with Pt(II) units for targeted tumor applications are synthesized by post-polymerization modification of poly(2-ethyl-2-oxazoline-block-2-(3-butenyl)-2-oxazoline) using thiol-ene photoaddition. The hemolytic activity, induction of erythrocyte aggregation as well as the cytotoxicity against mouse fibroblast L929 cells, human embryonic kidney cells HEK 293, and human hepatocytes HepG2 is studied and compared with cisplatin.

    18. ABA triblock copolymers from two mechanistic techniques: Polycondensation and atom transfer radical polymerization

      Natalia A. Agudelo, Andrea M. Elsen, Hongkun He, Betty L. López and Krzysztof Matyjaszewski

      Article first published online: 9 JUL 2014 | DOI: 10.1002/pola.27300

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      A series of ABA triblock copolymers were synthesized utilizing two polymerization techniques, polycondensation and atom transfer radical polymerization (ATRP). The choice of polymerization mechanisms results in block copolymers with unique molecular weight distributions the center of these triblock copolymers are disperse, resulting from polycondensation while the outside blocks have narrow molecular weight distribution due to the control afforded from ATRP.

    19. Synthesis, self-assembly, and thermosensitivity of amphiphilic POEGMA-PDMS-POEGMA triblock copolymers

      Guiyou Wang, Mengli Chen, Shiqing Guo and Aiguo Hu

      Article first published online: 9 JUL 2014 | DOI: 10.1002/pola.27299

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      A well-defined biocompatible amphiphilic POEGMA-PDMS-POEGMA triblock copolymer was synthesized by atom transfer radical polymerization using α,ω-dibromo polydimethylsiloxane as a macroinitiator. The copolymers had good thermosensitivity, with reversible and sharp phase separation. The copolymers had low critical micelle concentration values and easily self-assembled into spherical micelles in aqueous solution.

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

      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.

    21. Synthesis of triarylamine-containing poly(arylene ether)s by nucleophilic aromatic substitution reaction

      Jinhee Lee, Jaewon Heo, Changjun Park, Byung-Kwon Kim, Juhyoun Kwak, Myungeun Seo and Sang Youl Kim

      Article first published online: 3 JUL 2014 | DOI: 10.1002/pola.27289

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      A series of new triarylamine-containing poly(arylene ethers) were synthesized via nucleophilic aromatic substitution reaction of AB-type monomers. By introducing electron-withdrawing groups at the para position of the nitrogen atom, it was possible to tune reactivity of the monomers as well as the optoelectric properties of the polymers. The resulting polymers also possessed good solublities and high thermal stabilities with glass transition temperatures up to 227 °C.

    22. A versatile A2 + B3 approach to hyperbranched polyacenaphthenequinones

      Jun-Yi Chen, Zi-Long Xiang, Feng Yu, Bert F. Sels, Yu Fu, Ting Sun, Mario Smet and Wim Dehaen

      Article first published online: 26 JUN 2014 | DOI: 10.1002/pola.27275

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      A series of hyperbranched polyacenaphthenequinones is prepared by a combination of superelectrophilic reaction and A2 + B3 approach. The molecular weight of the polymer can be tuned by adjusting the electron-withdrawing effect of the substituents of the A2 monomer. Further modification of the polymer is explored both on the acenaphthenequinone and aromatic moieties. The sulfonated polymer performs well for the degradation of cellulose.

    23. Investigation of catalyst-transfer condensation polymerization for synthesis of poly(p-phenylenevinylene)

      Masataka Nojima, Yoshihiro Ohta and Tsutomu Yokozawa

      Article first published online: 26 JUN 2014 | DOI: 10.1002/pola.27281

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      The feasibility of catalyst-transfer condensation polymerization of phenylenevinylene type monomers was investigated for the synthesis of well-defined poly(phenylenevinylene) (PPV). Kumada-Tamao coupling polymerization with a Ni catalyst afforded PPV with low molecular weight. On the other hand, Suzuki-Miyaura coupling polymerization with a Pd catalyst yielded PPV with high molecular weight. However, the molecular weight distribution was broad, and the MALDI-TOF mass spectra showed the peaks of polymers bearing no initiator unit at the chain end.

    24. Synthesis of cyclic olefin polymers with high glass transition temperature by ring-opening metathesis (Co)Polymerization and subsequent hydrogenation

      Ji-Xing Yang, Jing Cui, Ying-Yun Long, Yan-Guo Li and Yue-Sheng Li

      Article first published online: 25 JUN 2014 | DOI: 10.1002/pola.27283

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      A series of high-performance cyclic olefin polymers derived from exo-1,4,4a,9,9a,10-hexahydro-9,10(1′,2′)-benzeno-l,4-methanoanthracene with high glass transition temperature (Tg = up to 220 °C), excellent transparency (transmittance, >88%), and improved mechanical performance (strain at break, 3–5%) have synthesized via ring-opening metathesis polymerization and subsequent complete hydrogenation.

    25. Synthesis and self-assembly of stimuli-responsive amphiphilic block copolymers based on polyhedral oligomeric silsesquioxane

      Lizhi Hong, Zhenghe Zhang, Yuan Zhang and Weian Zhang

      Article first published online: 24 JUN 2014 | DOI: 10.1002/pola.27287

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      Stimuli-responsive amphiphilic diblock copolymers of PHEMPOSS-b-PDMAEMA with a high DP of POSS unit were synthesized via RAFT polymerization. The self-assembled morphologies of PHEMAPOSS-b-PDMAEMA in aqueous solution can be tuned from irregular assembled aggregates to spherical core-shell micelle and further from pearl-necklace-liked structure to large compound vesicles by varying the length of hydrophilic PDMAEMA block chain.

    26. Functional off-stoichiometry thiol-ene-epoxy thermosets featuring temporally controlled curing stages via an UV/UV dual cure process

      Carl Fredrik Carlborg, Alexander Vastesson, Yitong Liu, Wouter van der Wijngaart, Mats Johansson and Tommy Haraldsson

      Article first published online: 23 JUN 2014 | DOI: 10.1002/pola.27276

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      Thiol-ene-epoxy thermosets are polymerized in a two-stage UV/UV curing process. The curing stages are temporally separated up to 24 h by using two different photoinitiators, activated at different wavelengths. The polymers feature distinctly different mechanical and chemical properties after each curing stage. After the first cure, a soft thiol-ene network is formed with unreacted thiol and epoxy groups being present in the network. After the second cure, a stiff highly crosslinked thiol-ene-epoxy network is formed.

    27. Well-controlled RAFT polymerization initiated by recyclable surface-modified Nb(OH)5 nanoparticles under visible light irradiation

      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 the 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 for many times without significant decrease of initiation efficiency.

  7. Rapid Communications

    1. UV-reversible chain extendable polymers from thymine functionalized telechelic polymer chains

      Gagan Kaur, Arthur Bertrand, Julien Bernard, Toby D. M. Bell and Kei Saito

      Article first published online: 23 JUN 2014 | DOI: 10.1002/pola.27282

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      The ability of thymine to photodimerize has been exploited to synthesize a reversibly chain-extendable polymer system. The photopolymerization (>270 nm) of α,ω-thymine functionalized poly(n-butyl acrylate) (Thy-PnBuA-Thy) oligomers was successfully carried out in solid film state. These polymers were further successfully depolymerized by using shorter wavelength UV irradiation (<250 nm). These studies demonstrate a novel method to synthesize linear reversibly chain-extendable polymers based on photodimerization of terminally thymine functionalized oligomers.

  8. Articles

    1. Well-defined phosphonate-functional copolymers through RAFT copolymerization of dimethyl-p-vinylbenzylphosphonate

      Issam Blidi, Olivier Coutelier and Mathias Destarac

      Article first published online: 20 JUN 2014 | DOI: 10.1002/pola.27277

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      Dibenzyltrithiocarbonate-mediated RAFT polymerization of dimethyl-p-vinylbenzylphosphonate and its copolymerization with styrene allowed the controlled synthesis of statistical, di-, and triblock copolymers of controlled molar mass, low dispersities, and tunable amount and location of dimethylphosphonate groups along the chain. Different postpolymerization treatments were developed in order to obtain phosphonic acid-functional diblock or triblock copolymers from one single phosphonate ester triblock precursor.

    2. Facile anionic synthesis of well-defined block copolymers with pendent triphenylamine and ethynylpyridine for nonvolatile memory device applications with high performances

      Beom-Goo Kang, Sunghoon Song, Byungjin Cho, Nam-Goo Kang, Myung-Jin Kim, Takhee Lee and Jae-Suk Lee

      Article first published online: 20 JUN 2014 | DOI: 10.1002/pola.27278

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      The well-defined functional block copolymers containing A block as an electron donor and B block as a weak electron acceptor (PBAB) were simply synthesized by using only potassium naphthalenide (K-Naph) initiator with K+ countercation in the absence of any additives. The memory device fabricated with the well-defined PBAB exhibiting bicontinuous microphase-separated morphology showed high performances with regard to nonvolatile memory characteristics.

  9. Highlight

    1. Optimization of direct arylation polymerization (DArP) through the identification and control of defects in polymer structure

      Andrey E. Rudenko and Barry C. Thompson

      Article first published online: 20 JUN 2014 | DOI: 10.1002/pola.27279

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      Just like any other method of polymerization, direct arylation polymerization (DArP) produces defects in polymer structure, which have a strong impact on polymer properties. Therefore, it is important for polymer scientists to understand what causes the defect formation and how to control them. DArP produces four major classes of defects, and here we discuss in detail the origin of defects, their influence on polymer properties and the available methods to control them.

  10. Articles

    1. Platinum-segmented polydiacetylenes

      Keda Hu, Elena Pandres and Yang Qin

      Article first published online: 19 JUN 2014 | DOI: 10.1002/pola.27286

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      These platinum-segmented polydiacetylenes (Pt-PDAs) represent a new series of conjugated polymers by replacing every other double bond along PDA backbones with a Pt center and placing two fully conjugated aromatic substituents at every remaining double bond. Physical and electronic properties of resulting polymers are systematically tunable through such structural design.

    2. Synthesis, structural characterization, and ethylene polymerization behavior of (arylimido)vanadium(V) complexes bearing tridentate Schiff base ligands

      Ling-Pan Lu, Jia-Bao Wang, Jing-Yu Liu and Yue-Sheng Li

      Article first published online: 19 JUN 2014 | DOI: 10.1002/pola.27280

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      A series of novel (arylimido)vanadium(V) complexes bearing tridentate salicylaldiminato chelating ligands have been synthesized, characterized, and investigated as the precatalysts for ethylene polymerization. The maximum activities displayed by [ONP]-'based (arylimido)vanadium(V) complex at high temperature (75°C) are relatively high values exhibited by homogeneous vanadium(V) catalysts.

    3. Synthesis and proton conductivity of sulfonated, multi-phenylated poly(arylene ether)s

      Hsu-Feng Lee, Po-Hsun Wang, Yi-Chiang Huang, Wen-Hung Su, Ram Gopal, Chun Che Lee, Steven Holdcroft and Wen-Yao Huang

      Article first published online: 19 JUN 2014 | DOI: 10.1002/pola.27273

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      Sulfonated, multiphenylated, random copolymers of poly(arylene ether)s were synthesized for examination as proton-conducting membranes. Proton conductivities ranged from 3 to 167 mS/cm at 80 °C/95% RH. The highly-encumbered polymer framework conferred exceptional mechanical strength and dimensional stability.

    4. Cuso4-amine redox-initiated radical polymerization of methyl methacrylate mediated by CuCl2 complex: Homogeneous reverse ATRP

      Jie Gao, Wan Song, Peng Wang and Guangqun Zhai

      Article first published online: 16 JUN 2014 | DOI: 10.1002/pola.27272

      Thumbnail image of graphical abstract

      CuII/L complex oxidizes tertiary amines such as triethylamine into aminoalkyl radicals to initiate polymerization of MMA in the presence of CuCl2/L, constituting redox-initiated homogeneous reverse ATRP. Both initiator efficiency of amines and MW of PMMA increase gradually with conversions. Such a facile protocol leads to heterochelic bifunctional PMMA of alpha amino and omega C-Cl functionality.

    5. Transformation of sulfur to organic–inorganic hybrids employed by networks and their application for the modulation of refractive indices

      Kazuo Tanaka, Honami Yamane, Koji Mitamura, Seiji Watase, Kimihiro Matsukawa and Yoshiki Chujo

      Article first published online: 13 JUN 2014 | DOI: 10.1002/pola.27274

      Thumbnail image of graphical abstract

      The network polymers with the polysulfide-bridged polyhedral oligomeric silsesquioxane were synthesized and mixed with polystyrene and poly(methyl methacrylate) to corm hybrid materials with elemental sulfur. The resulting hybrid materials showed higher thermal stability than those of polymers. In addition, it was found that the sulfur-bridging networks can increase refractive indices of the polymer matrices. Interestingly, the loss of Abbe numbers was hardly observed.

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