Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 50 Issue 20

15 October 2012

Volume 50, Issue 20

Pages i–iv, 4155–4368

  1. Cover Image

    1. Top of page
    2. Cover Image
    3. Rapid Communication
    4. Articles
    5. Notes
    6. Erratum
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      Cover Image, Volume 50, Issue 20 (pages i–ii)

      Version of Record online: 6 SEP 2012 | DOI: 10.1002/pola.26351

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      Inspired by nature, optically active polymeric materials obtained synthetically have been of particular interest in the area of modern polymer science. On page 4215, Mariliz Achilleos, Demetris Kafouris, Simon J. Holder, and Theodora Krasia-Christoforou describe a simple and cost-effective methodology for the preparation of a new optically active monomer, namely (S)-(+)-2-methyl-1-butyl methacrylate. The latter is employed to prepare well-defined optically active methacrylic diblock copolymers by reversible addition-fragmentation chain transfer (RAFT) polymerization. This straightforward and undemanding approach opens up a new pathway towards the design and synthesis of optically active polymers characterized by structural simplicity.

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      Inside Cover, Volume 50, Issue 20 (pages iii–iv)

      Version of Record online: 6 SEP 2012 | DOI: 10.1002/pola.26352

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      Novel oxidative coupling polycondensation is developed. When bishydrazide is treated with oxone, poly(diacylhydrazine) (PDAH) is obtained. Although PDAH exhibits high thermal stability in air, PDAH is rapidly oxidized and degraded to the corresponding dicarboxylic acid upon treatment with sodium hypochlorite. Therefore, an oxidatively degradable high-performance polymer is obtained by oxidation, as presented by Kentaro Nagashima, Nobuhiro Kihara, and Yusuke Iino on page 4230. The first stage of the cover image indicates the oxidative coupling of hydrazide with oxone (persulfate anion) to form bishydrazide, releasing nitrogen and water. The second stage indicates the oxidation of polymer with hypochlorite anion to form dicarboxylic acid and nitrogen.

  2. Rapid Communication

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    2. Cover Image
    3. Rapid Communication
    4. Articles
    5. Notes
    6. Erratum
    1. (N-heterocyclic carbene)-Pd catalyzed synthesis of poly(triarylamine)s by Buchwald-Hartwig coupling of aryl chlorides (pages 4155–4160)

      Mario Hoyos, Reiner Sebastian Sprick, Chao Wang, Michael Lewis Turner and Oscar Navarro

      Version of Record online: 25 JUL 2012 | DOI: 10.1002/pola.26239

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      The use of an air and moisture stable, commercially available (N-heterocyclic carbene)-Pd complex as precatalyst allows for the unprecedented Buchwald-Hartwig polyamination of aryl chlorides with primary amines. Different approaches for the end-capping of the polymers have also been evaluated.

  3. Articles

    1. Top of page
    2. Cover Image
    3. Rapid Communication
    4. Articles
    5. Notes
    6. Erratum
    1. New copolymers of a tautomerizable β-ketonitrile monomer: Synthesis, characterization and solution tautomerism (pages 4161–4169)

      Juan M. Giussi, Patricia E. Allegretti and M. Susana Cortizo

      Version of Record online: 20 JUL 2012 | DOI: 10.1002/pola.26238

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      Copolymers of a tautomerizable β-ketonitrile monomer and styrene were synthesized, which exhibited keto-enol tautomerism and the shift of equilibrium depend on solvent polarity. In acetonitrile the enol proportion was higher than chloroform as was demonstrated by NMR and FTIR studies. The intrinsic viscosity and hydrodynamic radius were different in both selected solvents. This difference was attributed to the higher proportion of enol form in acetonitrile, where the hydrogen-bondings intra-chain are responsible for the lowest hydrodynamic radius.

    2. Syntheses and properties of dumbbell-shaped POSS derivatives linked by luminescent π-conjugated units (pages 4170–4181)

      Hitoshi Araki and Kensuke Naka

      Version of Record online: 20 JUL 2012 | DOI: 10.1002/pola.26241

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      Dumbbell-shaped POSS derivatives linked by luminescent π-conjugated linkers and corresponding model compounds were synthesized, and their film formabilities and thermal and optical properties were examined. The dumbbell-shaped POSS compounds gave optical transparent films. These films emitted under UV irradiation. The dumbbell structures reduce longer wavelength shifts and improve emission efficiency of the luminescent π-conjugated linker units in their solid states compared with the model compounds.

    3. Thermo-sensitive electrospun fibers prepared by a sequential thiol-ene click chemistry approach (pages 4182–4190)

      Hong Yang, Qi Zhang, Baoping Lin, Guodong Fu, Xueqin Zhang and Lingxiang Guo

      Version of Record online: 20 JUL 2012 | DOI: 10.1002/pola.26244

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      A solvent-resistant electrospun fiber with a partially photo-crosslinked poly[3-mercaptopropylmethylsiloxane] (PMMS) backbone and poly(N-isopropylacrylamide) (PNIPAM) brushes have been developed. By controlling the molar ratio of PMMS and the cross-linker, triallyl cyanurate (TAC), PMMS-based fibers can be partially photo-crosslinked via UV-initialized thiol-ene radical addition to grant them the solvent-resistant property, meanwhile leaving a lot of unreacted mercapto groups on the surfaces, which could be further functionalized with stimuli-responsive polymer brushes via thiol-ene Michael nucleophilic addition chemistry.

    4. A chiral polymer-based turn-on fluorescent sensor for specific recognition of hydrogen sulfate (pages 4191–4197)

      Dan Chen, Wei Lu, Ganhong Du, Liming Jiang, Jun Ling and Zhiquan Shen

      Version of Record online: 16 JUL 2012 | DOI: 10.1002/pola.26230

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      A chiral polymer-based sensor containing naphthalene signal moieties and imine recognition sites was synthesized by RAFT polymerization technique. It was found that the “turn-on” sensor exhibits a specific response toward hydrogen sulfate relative to other anions (including F, Cl, Br, H2PO4, CH3CO2, and NO3) in absorption, emission, and circular dichroism (CD) spectroscopy, accompanied by a noticeable colorless-to-pale yellow change. More interestingly, the HSO4-induced CD signal can be totally reversedwith addition of base and eventually recovered the initial state, leading to a chiroptical molecular switch with two distinguished “on” and “off” states.

    5. Synthesis and characterization of six-arm star polystyrene-block-poly (3-hexylthiophene) copolymer by combination of atom transfer radical polymerization and click reaction (pages 4198–4205)

      Dehui Han, Xia Tong and Yue Zhao

      Version of Record online: 29 JUN 2012 | DOI: 10.1002/pola.26221

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      A new six-arm star diblock copolymer comprising polystyrene (PS) and regioregular poly(3-hexylthiophene) (P3HT) was synthesized. The preparation consists in using a six-functional atom transfer radical polymerization initiator to obtain star PS, converting bromine groups at chain ends into azide and click coupling PS with alkynyl-terminated P3HT. Characterization results indicate that the star architecture could impose a topological constraint effect on the microphase separation, resulting in morphology with larger domains as compared to linear PS-b-P3HT analogs.

    6. Poly(ε-caprolactone) by combined ring-opening polymerization and azeotropic polycondensation—the role of cyclization and equilibration (pages 4206–4214)

      Hans R. Kricheldorf, Steffen M. Weidner and Felix Scheliga

      Version of Record online: 9 JUL 2012 | DOI: 10.1002/pola.26222

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      Large amounts of cyclic poly(ε-caprolactone)s could be easily synthesized by a combination of ring-opening polymerization and azeotropic polycondensation. It is shownthat ring formation is almost exclusively a consequence of end-to-end cyclization (i.e. esterification step) and not of “back-biting” and equilibration.

    7. Synthesis and characterization of well-defined optically active methacrylic diblock copolymers (pages 4215–4222)

      Mariliz Achilleos, Demetris Kafouris, Simon J. Holder and Theodora Krasia-Christoforou

      Version of Record online: 9 JUL 2012 | DOI: 10.1002/pola.26223

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      The development of well-defined, optically active amphiphilic diblock copolymers characterized by structural simplicity is described for the first time. The synthetic methodology involves the transformation of a low-cost, optically active alcohol into a new optically active methacrylic monomer, namely, (S)-(+)-2-methyl-1-butyl methacrylate (S)-(+)-MBuMA. Using RAFT polymerization, a series of well-defined p((S)-(+)-MBuMA) homopolymers, as well as diblock copolymers with the water-soluble and ionizable 2-(dimethyl amino)ethyl methacrylate (DMAEMA) are prepared and characterized in terms of their molecular structure, self-assembly behavior in selective aqueous media, and optical activity.

    8. Synthesis and photophysical properties of polyethylene containing pyrenyl units in the side chain (pages 4223–4229)

      Naofumi Naga, Nobuo Tano and Haruhiko Tomoda

      Version of Record online: 9 JUL 2012 | DOI: 10.1002/pola.26224

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      Copolymerization of ethylene and diallyl-bis(pyren-1-yl)-silane (APyS) was investigated with zirconocene catalysts using methylaluminoxane as a cocatalyst. APyS was copolymerized via both 1,2-insertion and cyclization insertion. The resulting copolymer showed absorption and fluorescence derived from pyrenyl group. Chloroform solution of the copolymer showed emission derived from both monomer and eximer of pyrenyl units. Only the emission derived from eximer of pyrenyl units was observed in the cast film. The polarized photoluminescence spectrum of an oriented film showed anisotropy, and the polarization excitation parallel to the drawing direction showed high fluorescence intensity.

    9. Oxidative coupling polymerization of bishydrazide for the synthesis of poly(diacylhydrazine): Oxidative preparation of oxidatively degradable polymer (pages 4230–4238)

      Kentaro Nagashima, Nobuhiro Kihara and Yusuke Iino

      Version of Record online: 9 JUL 2012 | DOI: 10.1002/pola.26225

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      The oxidative coupling polycondensation of bishydrazide affords poly(diacylhydrazine) (PDAH). Oxone is an effective oxidant. Use of an aprotic polar solvent, water, and acetonitrile or N,N-dimethylacetamide is necessary as the solvent. PDAH degrades by the action of sodium hypochlorite in water or hydrogen peroxide in acetonitrile-containing media to the corresponding carboxylic acid. PDAH exhibits high thermal stability in air (oxygen) and a high Tg value.

    10. Synthesis of mikto-topology star polymer containing one cyclic arm (pages 4239–4245)

      Xiubo Jiang, Yi Shi, Wen Zhu, Yongming Chen and Fu Xi

      Version of Record online: 9 JUL 2012 | DOI: 10.1002/pola.26226

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      Well-defined mikto-topology star polystyrene composed of one cyclic arm and four linear arms was synthesized. The methodology is a combination of sequential atom transfer radical polymerization, click reaction, and functionalities transformation using a multi-functionalized initiator.

    11. Constitutionally isomeric alicyclic polyimides: Origin of siteselectivity in the reaction of unsymmetrical dianhydride and structure-derived difference in physical properties (pages 4246–4254)

      Jiyoung Choi, Kazuaki Shirai, Toshio Takayama, Kengo Akagawa and Kazuaki Kudo

      Version of Record online: 16 JUL 2012 | DOI: 10.1002/pola.26231

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      Origin of siteselective reactivity of an unsymmetric spiroalicyclic dianhydride, rel-[1R,5S,6R]-3-oxabicyclo[3,2,1]octane-2,4-dione-6-spiro-3′-(tetrahydrofuran-2′,5′-dione), was clarified by means of the ring opening reaction of model anhydrides. Several sets of head-to-head (HH) and random polyimides were prepared using this dianhydride by changing polymerization method. HH polyimides showed higher glass transition temperature and higher dielectric constant than random counterparts regardless of the kind of diamines used.

    12. Aqueous developable dual switching photoresists for nanolithography (pages 4255–4265)

      Lan Chen, Yong Keng Goh, Han Hao Cheng, Bruce W. Smith, Peng Xie, Warren Montgomery, Andrew K. Whittaker and Idriss Blakey

      Version of Record online: 16 JUL 2012 | DOI: 10.1002/pola.26232

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      Photon-mediated switching of polymer solubility plays a crucial role in the photolithographic process. Conventional photoresists typically rely on a single switching mechanism, which is usually based on a change in polarity or molecular weight. A photoresist platform is reported that uses both these mechanisms, such that the irradiated polymer becomes soluble in aqueous base. The 193 nm photochemistry of the polymer thin films was followed using advance analytical techniques. The nanoscale patterning performance of the polymers was also assessed using 193 nm interference lithography and electron beam lithography.

    13. An acceptor-acceptor conjugated copolymer based on perylene diimide for high mobility n-channel transistor in air (pages 4266–4271)

      Xingang Zhao, Yugeng Wen, Longbin Ren, Lanchao Ma, Yunqi Liu and Xiaowei Zhan

      Version of Record online: 16 JUL 2012 | DOI: 10.1002/pola.26233

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      The first air-stable A-A type conjugated copolymer P1 based on PDI was synthesized by incorporating electron-deficient fluorenone in the polymer main chain. Relative to the D-A type conjugated polymer P2, polymer P1 exhibits 0.1 eV down shift of LUMO level, 70 nm blue shift of low-energy absorption band, and 0.36 eV increase of optical band gap. An electron mobility of 0.01 cm2/(V s) was achieved in P1-based bottom-gate top-contact OFETs in ambient atmosphere, while P2 showed complete inactivity in the same devices in air.

    14. New ladder-type conjugated polymer with broad absorption, high thermal stability, and low band gap (pages 4272–4276)

      Shitao Wang, Wei Hong, Shendong Ren, Jie Li, Mao Wang, Xike Gao and Hongxiang Li

      Version of Record online: 16 JUL 2012 | DOI: 10.1002/pola.26234

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      A new conjugated ladder type polymer poly{6-alkyl-pyrrolo[3,2-b:4,5-b′]bis-[1,4]benzothi-azine} (PPBBTZ) was synthesized in facile method. Experimental results showed PPBBTZ displayed high thermal stability, low band gap, and broad absorption.

    15. Core–shell nanogels by RAFT crosslinking polymerization: Synthesis and characterization (pages 4277–4287)

      Lorenzo A. Picos-Corrales, Angel Licea-Claveríe and Karl-Friedrich Arndt

      Version of Record online: 16 JUL 2012 | DOI: 10.1002/pola.26235

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      The reversible addition-fragmentation chain transfer technique was used to prepare core–shell nanogels with large crosslinked core by radical crosslinking copolymerization in homogeneous phase. A dithiobenzoate (CTA) with a terminal [BOND]OH group was used to prepare macro-CTAs from PNIPAAm or statistical copolymers (N-isopropylacrylamide/acid comonomers) with prescribed molecular weights. Macro-CTA and a mixture of divinylbenzene and comonomers ((meth)acrylates) were used to synthesize core–shell nanogels with large hydrophobic functionalized core. The comonomers in the core provide the nanogels with functional groups for specific interactions with small molecules. Nanogels were soluble in organic medium and dispersible in aqueous medium. These macromolecules have potential application as catalytic scaffolds.

    16. Biohybrid nanogels by crosslinking of ovalbumin with reactive star-PEGs in W/O emulsions (pages 4288–4299)

      Smriti Singh, Julia Blöhbaum, Martin Möller and Andrij Pich

      Version of Record online: 16 JUL 2012 | DOI: 10.1002/pola.26236

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      Biohybrid nanogels with variable size and protein loading were synthesized by crosslinking six-arm acrylate-functionalized star-shaped P(EO-stat-PO) with the amine groups of the hen egg ovalbumin in W/O emulsion.

    17. Hybrid amphiphilic block copolymers containing polyhedral oligomeric silsesquioxane: Synthesis, characterization, and self-assembly in solutions (pages 4300–4310)

      Cangjie Yang, Yuanming Deng, Birong Zeng, Conghui Yuan, Min Chen, Weiang Luo, Jie Liu, Yiting Xu and Lizong Dai

      Version of Record online: 20 JUL 2012 | DOI: 10.1002/pola.26237

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      Well-defined hybrid amphiphilic diblock copolymers, namely PMAPOSS-b-P(AA-co-St), were synthesized by the combination of RAFT and hydrolysis. The self-assembly morphology in solutions like spheres-dispersed, onion-like, onion-cluster, core-shell spherical, and disordered nanoparticles can be controlled via lengths of both blocks, composition of the co-block and the external parameter like the selective solvent.

    18. UCST and LCST phase behavior of poly(trimethylene ether) glycol in water (pages 4311–4315)

      Hau-Nan Lee, Brad M. Rosen, Gyorgyi Fenyvesi and Hari B. Sunkara

      Version of Record online: 20 JUL 2012 | DOI: 10.1002/pola.26242

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      The complex aqueous phase behavior of poly(trimethylene ether) glycol (PO3G), a renewably sourced polyether glycol, is described. PO3G exhibits both lower critical solution temperature (LCST) and upper critical solution temperature (UCST) in water in the temperature range between 30°C and 80°C. Both the LCSTs and UCSTs can be easily tuned over a wide range by varying the amount of alcohol co-solvents. These findings have potential applications in the design of thermosensitive “smart” materials.

    19. Synthesis and optoelectronic properties of novel benzodifuran semiconducting polymers (pages 4316–4324)

      Prakash Sista, Peishen Huang, Samodha S. Gunathilake, Mahesh P. Bhatt, Ruvini S. Kularatne, Mihaela C. Stefan and Michael C. Biewer

      Version of Record online: 20 JUL 2012 | DOI: 10.1002/pola.26243

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      Two new semiconducting polymers of benzodifuran with decylphenylethynyl substituents were synthesized. These polymers were tested in bulk heterojunction solar cells. The surface morphology of the solar cell devices was investigated and correlated to the solar cell performance.

    20. Synthesis and characterization of thiol–ene functionalized siloxanes and evaluation of their crosslinked network properties (pages 4325–4333)

      Megan A. Cole and Christopher N. Bowman

      Version of Record online: 20 JUL 2012 | DOI: 10.1002/pola.26245

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      Thiol-ene chemistry is exploited in the network formation of functionalized siloxane oligomers. By varying the structural composition of both the thiol- and ene-functionalized oligomer, the elastomeric properties, mechanical strength, and surface energy of the photopolymerized material are controlled. Nonreactive phenyl-functional repeat units within the siloxane oligomer increased the glass transition temperature, elasticity, and toughness. The increasing presence of octyl-functional repeats produced crosslinked networks with increasingly hydrophobic surfaces.

    21. Polymer electrolyte membranes based on polystyrenes with phosphonic acid via long alkyl side chains (pages 4334–4340)

      Youko Tamura, Li Sheng, Satoshi Nakazawa, Tomoya Higashihara and Mitsuru Ueda

      Version of Record online: 20 JUL 2012 | DOI: 10.1002/pola.26246

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      The synthesis of polystyrenes with phosphonic acid via long alkyl side chains with ion exchange capacity (IEC) from 3.00 to 3.80 mequiv/g and the membrane properties, such as proton conductivity, water uptake, and oxidative stability have been investigated.

    22. pH- and temperature-sensitive statistical copolymers poly[2-(dimethylamino)ethyl methacrylate-stat-2-vinylpyridine] with Functional succinimidyl-ester chain ends synthesized by nitroxide-mediated polymerization (pages 4341–4357)

      Chi Zhang and Milan Maric

      Version of Record online: 20 JUL 2012 | DOI: 10.1002/pola.26247

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      This article describes a series of statistical copolymerizations of 2-(dimethylamino)ethyl methacrylate with 1 to 20 mol % 2-vinylpyridine in the feed utilizing a succinimidyl ester-terminated BlocBuilder at 80 °C. All copolymerizations occurred in a controlled manner with no additional SG1 free nitroxide. The initiator was conjugated to amine-terminated poly(propylene glycol), yielding an effective macroinitiator for synthesizing a block copolymer. Thermo- and pH-sensitivities of the statistical and block copolymers are comprehensively studied by UV–vis spectroscopy and dynamic light scattering.

    23. Copper-mediated initiators for continuous activator regeneration atom transfer radical polymerization of acrylonitrile (pages 4358–4364)

      Xiao-hui Liu, Jin Wang, Fei-jun Zhang, Shu-lin An, Yuan-lin Ren, Yun-hai Yu, Peng Chen and Shan Xie

      Version of Record online: 20 JUL 2012 | DOI: 10.1002/pola.26248

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      Initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP) technique were first accessed to acrylonitrile by using CuBr2/2,2′-bipyridine as the catalyst, ethyl 2-bromoisobutyrate as the halogen initiator, and azobis(isobutyronitrile) as the free radical initiator. The key to success is ascribed to the facile achievement of the rapid equilibrium between active species and dormant species. The polymerization proceeded in a controlled/living fashion even though the concentration of the copper catalyst decreased to 50 ppm, which is evident in pseudo first-order kinetics of polymerization, linear increase of molecular weight, low PDI, and high chain-end functionality of the generated polymer.

  4. Notes

    1. Top of page
    2. Cover Image
    3. Rapid Communication
    4. Articles
    5. Notes
    6. Erratum
    1. You have free access to this content
      Development of high-performance networked polymers based on cyclotrimerization of isocyanates: Control of properties by addition of monoisocyanates (pages 4365–4367)

      Masaki Moritsugu, Atsushi Sudo and Takeshi Endo

      Version of Record online: 20 JUL 2012 | DOI: 10.1002/pola.26240

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      Highly heat-resistant networked polymers consisting of isocyanurate moieties have been developed based on cyclotrimerization of isocyanates. To the polymerization system using methylene diphenyl 4,4′-diisocyanate (MDI) as the main component, a series of aromatic monoisocyanates (p-tolylisocyanate, p-trifluoromethylphenylisocyanate, p-tert-butylphenylisocyanate, and p-butylphenylisocyanate) were added with varying feed ratio [MDI]0:[monoisocyanate]0 to achieve successful control of flexibility of thecorresponding networked polymers without serious deterioration of the thermal stability.

  5. Erratum

    1. Top of page
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    3. Rapid Communication
    4. Articles
    5. Notes
    6. Erratum
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      Phospha-Michael addition to enone-containing triglyceride derivatives as an efficient route to flame retardant renewable thermosets (page 4368)

      Maryluz Moreno, Gerard Lligadas, Joan C. Ronda, Marina Galià and Virginia Cáldiz

      Version of Record online: 5 JUL 2012 | DOI: 10.1002/pola.26227

      This article corrects:

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