Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 51 Issue 16

15 August 2013

Volume 51, Issue 16

Pages i–iv, 3323–3530

  1. Cover Image

    1. Top of page
    2. Cover Image
    3. Rapid Communications
    4. Articles
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      Cover Image, Volume 51, Issue 16 (pages i–ii)

      Article first published online: 2 JUL 2013 | DOI: 10.1002/pola.26826

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      The pH and temperature responsive behavior of random copolymers of dimethylaminoethyl acrylate (DMAEA) and methyl acrylate (MA) and their methacrylate counterparts (DMAEMA and MMA) is studied in aqueous solution by Pepa Cotanda, Daniel B. Wright, Martin Tyler, and Rachel K. O'Reilly on page 3333. The higher incorporation of the hydrophobic monomer in the copolymer results in an increase in the pKa values due to the larger distance between charges, thus facilitating the protonation of adjacent nitrogens for both the acrylate and methacrylate derivatives. The cloud point values are irreproducible for the acrylate polymers due to the self-hydrolysis of DMAEA and kinetic studies are performed in order to explore the full potential of these versatile polymers.

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      Inside Cover, Volume 51, Issue 16 (pages iii–iv)

      Article first published online: 2 JUL 2013 | DOI: 10.1002/pola.26827

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      On page 3359, Michael Lartey, Martijn Gillissen, Brian J. Adzima, Kenichi Takizawa, David R. Luebke, and Hunaid B. Nulwala investigate polymerization behavior of regioisomeric vinyl triazole monomers with styrene. The results obtained for the reactivity ratio between regioisomers show exceptionally different polymerization behavior, highlighting the effects of the electronic and steric factors of these regioisomeric monomers. In the absence of any steric effects or electronic effects, a random copolymer is formed. The image shows that by selection of different functional groups and by the position of those functional groups on the monomer of vinyl-triazoles, the reactivity can be tuned from completely random toward an alternating polymer.

  2. Rapid Communications

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    2. Cover Image
    3. Rapid Communications
    4. Articles
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      Single electron transfer–living radical polymerization of acrylonitrile catalyzed by lanthanum powder (pages 3323–3327)

      Jiang Zhang, Zhihai Hao and Hou Chen

      Article first published online: 29 MAY 2013 | DOI: 10.1002/pola.26749

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      Synthesis of polyacrylonitrile (PAN) via single electron transfer–living radical polymerization in N,N-dimethylformamide with carbon tetrachloride as a initiator and La(0)/hexamethylenetetramine as catalyst system was discussed. The living nature of the polymerization was confirmed by the first-order kinetics of polymerization, linear increase of molecular weight with respect to conversion, and narrow molecular weight distribution. With an increase of La(0) content, monomer conversion, molecular weights of PAN, and their polydispersity increased.

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      Synthesis of high performance polyacrylonitrile by RASA SET–LRP in the presence of Mg powder (pages 3328–3332)

      Hou Chen, Gaojian Lv, Ying Liang and Jinming Sun

      Article first published online: 27 MAY 2013 | DOI: 10.1002/pola.26750

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      High-performance PAN was prepared with Mg powder as both reducing agent and supplemental activator by RASA SET–LRP. First-order kinetics of polymerization with respect to monomer concentration, linear increase of molecular weight and narrow polydispersity with monomer conversion, and the obtained high isotacticity PAN indicate that RASA SET–LRP in the presence of Mg powder could simultaneously control molecular weight and tacticity of PAN. Compared with that obtained with ascorbic acid (VC) as reducing agent, the increase in isotacticity of PAN was observed. The block copolymer PAN-b-PAN with molecular weight at 112460, polydispersity at 1.33, and isotacticity at 0.314 was successfully prepared.

  3. Articles

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

      A comparative study of the stimuli-responsive properties of DMAEA and DMAEMA containing polymers (pages 3333–3338)

      Pepa Cotanda, Daniel B. Wright, Martin Tyler and Rachel K. O'Reilly

      Article first published online: 6 JUN 2013 | DOI: 10.1002/pola.26730

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      Reversible addition-fragmentation chain transfer copolymerization of dimethylaminoethyl acrylate and methyl acrylate and their methacrylate counterparts has been performed with good control over molecular weight and polydispersity. The behavior of these pH and temperature-sensitive copolymers has been studied in aqueous solution by measuring the stability, cloud point and the acid dissociation constants (pKa). Interestingly a higher incorporation of hydrophobic monomer in the copolymer resulted in an increase in the pKa values.

    2. Synthesis and characterization of polythiophene block copolymer and fullerene derivative capable of “three-point” complementary hydrogen bonding interactions and their application in bulk-heterojunction solar cells (pages 3339–3350)

      Fei Li, Jianzhong Yang and Yang Qin

      Article first published online: 16 MAY 2013 | DOI: 10.1002/pola.26731

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      A “rigid-rod bottle-brush” type conjugated copolymer–fullerene composite has been obtained through “three-point” complementary hydrogen bonding interactions between a selectively functionalized polythiophene block copolymer and a novel thymine tethered fullerene derivative. Such non-covalent interactions allow facile tuning of fullerene loading percentages and the relatively high binding strengths lead to solid-state morphology stabilization. Solar cells fabricated from the “rigid-rod bottle-brush” composite were studied in detail. Benchmark P3HT/PCBM BHJ device performance and thermal stability could be improved by adding a few percentage of polymer/fullerene composite.

    3. Spotlight Article

      Effect of temperature and solvent on polymer tacticity in the free-radical polymerization of styrene and methyl methacrylate (pages 3351–3358)

      Leesa M. Smith and Michelle L. Coote

      Article first published online: 27 MAY 2013 | DOI: 10.1002/pola.26745

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      Bulk free-radical polymerization of nonbulky monomers normally offers scant prospects for controlling the tacticity or stereoregularity of the resulting polymer. To help understand this behavior and provide benchmark values for polymer tacticity, the effects of temperature and solvent on polymer tacticity have been studied for styrene and methyl methacrylate polymerizations. In both cases, the tacticities are relatively insensitive to solvent but show qualitatively different sensitivities to temperature.

    4. Synthesis and reactivity ratios of regioisomeric vinyl-1,2,3-triazoles with styrene (pages 3359–3364)

      Michael Lartey, Martijn Gillissen, Brian J. Adzima, Kenichi Takizawa, David R. Luebke and Hunaid B. Nulwala

      Article first published online: 16 MAY 2013 | DOI: 10.1002/pola.26723

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      This work investigates polymerization behavior of regioisomeric vinyl triazole monomers with styrene. The results obtained for the reactivity ratio between regioisomers show exceptionally different polymerization behavior highlighting the effects of the electronic and steric factors of these regioisomeric monomers. In the absence of any steric effects or electronic effects, a random copolymer is formed.

    5. Spotlight Article

      Thermally amendable tailor-made functional polymer by RAFT polymerization and “click reaction” (pages 3365–3374)

      Nabendu B. Pramanik, Dibyendu S. Bag, Sarfaraz Alam, Golok B. Nando and Nikhil K. Singha

      Article first published online: 21 MAY 2013 | DOI: 10.1002/pola.26732

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      Well-defined PFMA was successfully synthesized by reversible addition fragmentation chain-transfer (RAFT) polymerization using CDTSPA and 4 cyano-4-(thiobenzoylthio) pentanoic acid (CTBPA) as different chain transfer agents (CTA). Thereafter, the reactive furfuryl group of PFMA was used to prepare crosslinked polymeric materials via DA reaction using different bismaleimides. These crosslinked polymers showed thermally amendable properties through DA and retro-DA click reaction only by applying temperature.

    6. Synthesis and characterization of functionalized poly(ɛ-caprolactone) (pages 3375–3382)

      Jonathan Johannes Wurth and Venkatram Prasad Shastri

      Article first published online: 22 MAY 2013 | DOI: 10.1002/pola.26734

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      In this work, a new paradigm to functionalize poly(ɛ-caprolactone) using α,ω-epoxy esters is demonstrated. The model α,ω-epoxy ester, ethyl 2-methyl-4-pentenoate oxide (EMPO), was synthesized via epoxidation and its incorporation into the PCL backbone via ring-opening copolymerization was investigated. Statistical, random copolymers of CL and EMPO were obtained and copolymerization parameters were determined to be 1.31 and 0.01 for ɛ-caprolactone and EMPO, respectively.

    7. Spotlight Article

      Synthesis and properties of butyl rubber–poly(ethylene oxide) graft copolymers with high PEO content (pages 3383–3394)

      Solmaz Karamdoust, Colin V. Bonduelle, Ryan C. Amos, Bethany A. Turowec, Sharon Guo, Lorenzo Ferrari and Elizabeth R. Gillies

      Article first published online: 16 MAY 2013 | DOI: 10.1002/pola.26733

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      Butyl rubber–poly(ethylene oxide) (PEO) graft copolymers were synthesized through the derivatization of the isoprene moieties in butyl rubber containing high (7 mol %) isoprene content. Films of these graft copolymers exhibited interesting properties such as high stability in aqueous solution and resistance to the growth of cells at high PEO content. The copolymers also formed stable nanosized assemblies in aqueous solution and their size could be controlled through their preparation method.

    8. Electrically driven self-healing polymers based on reversible guest–host complexation of β-cyclodextrin and ferrocene (pages 3395–3403)

      Tsai-Wei Chuo, Ta-Chin Wei and Ying-Ling Liu

      Article first published online: 23 MAY 2013 | DOI: 10.1002/pola.26736

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      The reversible complexation reaction of ferrocene and β-cyclodextrin has been applied for preparation of electrically driven self-healing polymers. Addition of 20 wt % of this agent to a commercial car-painting product successfully brings self-healing properties to the coating product.

    9. Capture and release of CO2 by polyamidine (pages 3404–3411)

      Yoshio Furusho and Takeshi Endo

      Article first published online: 16 MAY 2013 | DOI: 10.1002/pola.26737

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      CO2 capturing and releasing behavior of a linear polyamidine having a hexamethylene linker has been investigated in solution as well as in the solid state. The polyamidine captures and releases CO2 in an aqueous solution to the same level as a common polyamine, polyethyleneimine. In contrast, a binary system consisting of the polyamidine and polyethylene glycol absorbs CO2 much more efficiently than that with the polyethyleneimine and polyethylene glycol.

    10. Synthesis and properties of through-space conjugated polymers based on π–π stacked 1,3-biarylpropane tethering units (pages 3412–3419)

      Ryosuke Nomura, Ryota Moriai, Masaru Kudo, Tohru Hoshino, Jun-ichi Watanabe, Shigeaki Funyu, Ken-ich Ishitsuka and Sentaro Okamoto

      Article first published online: 22 MAY 2013 | DOI: 10.1002/pola.26738

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      Novel skipped-π polymers comprising π-components connected with 2-substituted trimethylene tethering units that exist as stair-like stacking substructures were synthesized and found to exhibit bathochromically shifted, broadened UV absorption with a unique lower-energy absorption band and largely red-shifted fluorescent emission owing to the extended π-conjugation resulting from through-space π–π interactions in the ground and excited states.

    11. Synthesis of superparamagnetic and thermoresponsive hybrid nanoparticles via surface-mediated RAFT polymerization of di(ethylene glycol) ethyl ether acrylate and (oligoethylene glycol) methyl ether acrylate (pages 3420–3428)

      Adem Zengin, Ugur Tamer and Tuncer Caykara

      Article first published online: 22 MAY 2013 | DOI: 10.1002/pola.26739

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      Superparamagnetic and thermoresponsive hybrid nanoparticles composed of poly[di(ethylene glycol) ethyl ether acrylate-co-(oligoethylene glycol) methyl ether acrylate] shell and magnetic Fe3O4 core were synthesized via surface-mediated RAFT polymerization. The hybrid nanoparticles exhibited excellent magnetic susceptibility (Ms ≊ 55.1–19.4 emu/g) and showed a temperature-responsive behavior as the temperature changed between 25 and 40°C.

    12. Steric hindrance effect on thermo-responsive behaviors of well-defined water-soluble semi-rigid polymers (pages 3429–3438)

      Peng Liu, Qian Tan, Liangbo Xiang and Hailiang Zhang

      Article first published online: 29 MAY 2013 | DOI: 10.1002/pola.26740

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      The steric hindrance effect on liquid crystalline properties and thermoresponsive behaviors of semi-rigid water-soluble polymers poly[bis(N-(2-hydroxypropyl) pyrrolidone) 2-vinylterephthalate] [P(2-HPPVTA)] and poly[bis(N-(1-methyl-2-hydroxyethyl) pyrrolidone) 2-vinylterephthalate] [P(1-M-2-HEPVTA)] were carefully investigated. From molecular structure, the steric hindrance of P(1-M-2-HEPVTA) is stronger than that of P(2-HPPVTA). The dynamic light scattering results demonstrated that the more significant molecular weight and concentration dependence on cloud point have been observed in P(2-HPPVTA) solution than in P(1-M-2-HEPVTA) solution. The differences in thermo-responsive behaviors between P(2-HPPVTA) and P(1-M-2-HEPVTA) resulted from the steric hindrance effect of their side groups.

    13. Nanofluid polyurethane/polyurea resins—thin films and clearcoats (pages 3439–3448)

      John Texter, Zhiming Qiu, Rene Crombez and Weidian Shen

      Article first published online: 22 MAY 2013 | DOI: 10.1002/pola.26741

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      Solvent-free nanofluid and prepolymer are air cured to produce a tough and transparent clearcoat. The solvent-free nanofluid is prepared by surface-modifying nanosilica (9–10 nm) with an ionic liquid type of organic salt and with reactive isothiocyanate. It is dissolved in a novel poly(propylene oxide) isophorone diisocyanate prepolymer, coated, and cured with atmospheric moisture at room temperature. The proportion of nanofluid (1–16%) tunes the moduli and produces nanocomposites harder (2×) to softer (½×) than the control.

    14. Dramatic enhancement of carbon nanotube dispersion in polyimide composites by a two-step amino functionalization approach (pages 3449–3457)

      Yaqin Chen, Baoping Lin, Hong Yang, Ying Sun and Xueqin Zhang

      Article first published online: 16 MAY 2013 | DOI: 10.1002/pola.26742

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      Amino functionalized multiwall carbon nanotubes (MWNTs) are obtained by two ways: conventional one-step method (Di-MWNT) and the improved two-step approach (NH2-MWNT). Comparing with Di-MWNT, NH2-MWNT shows more excellent dispersion and better compatibility in the polyimide (PI) matrix. NH2-MWNTs can form a connected network structure throughout the PI matrix, which gives the NH2-MWNT/PI composite film good conductivity, mechanical property, and thermal stability.

    15. Novel amphiphilic homopolymers containing meta- and para-pyridine moieties with living characteristics and their self-assembly (pages 3458–3469)

      Yoon-Hyung Hur, Nam-Goo Kang, Beom-Goo Kang, Yong-Guen Yu, Mohammed Changez and Jae-Suk Lee

      Article first published online: 29 MAY 2013 | DOI: 10.1002/pola.26743

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      Amphiphilic monomers containing the isomeric pyridine moieties 3-(4-vinylphenyl)pyridine (3VPPy) and 4-(4-vinylphenyl)pyridine (4VPPy) were synthesized and a living anionic polymerization of 3VPPy and 4VPPy was successfully performed under various conditions. Additionally, each amphiphilic homopolymer of P3VPPy and P4VPPy containing both a hydrophilic pyridine unit and a hydrophobic styrene unit was tested for self-assembly behavior in a mixed solvent (THF/water) and monitored with TEM and SEM.

    16. Storage stability and curing behavior of epoxy-dicyandiamide systems with carbonyldiimidazole-Cu (II) complexes as the accelerator (pages 3470–3476)

      Xiang Dong Liu, Chun Hua Zhao, Atsushi Sudo and Takeshi Endo

      Article first published online: 27 MAY 2013 | DOI: 10.1002/pola.26744

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      CDI-Cu (II) complexes with bromide and nitride counter anions were found to be not only very effective for the acceleration of epoxy-DICY systems, but also chemically stable at ambient temperature. The storage stability and the acceleration effect of the complexes are both better than that of fenuron, the widely used latent accelerator for DICY-epoxy curing systems.

    17. Low band-gap modulation of isoindigo-based copolymers toward high open-circuit voltage of polymer solar cells (pages 3477–3485)

      Meixiu Wan, Hongbing Zhu, Heqiu Deng, Le Jin, Jun Guo and Yuelong Huang

      Article first published online: 11 JUN 2013 | DOI: 10.1002/pola.26746

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      The HOMO levels based on IID unit-conjugated polymers could be easily tuned from −5.84 eV to −5.33 eV by increasing electron-donating abilities from fluorene, carbazole, thiophene, dithiophene to dithienosilole. However, the LUMO levels of all the copolymers are found to be fixed at about −3.6 eV. The polymer solar cells based on PIID-DTS as donor and PC70BM as acceptor exhibited a high Voc of 0.93 V and a primary power conversion efficiency of 2.45%.

    18. Synthesis and properties of amphoteric copolymer of 5-vinyltetrazole and vinylbenzyl phosphonic acid (pages 3486–3493)

      Hongting Pu, Haochuan Luo and Decheng Wan

      Article first published online: 7 JUN 2013 | DOI: 10.1002/pola.26747

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      The amphoteric copolymer of 5-vinyltetrazole and diisopropyl-p-vinylbenzyl phosphonic acid is synthesized via free radical polymerization, which exhibits considerable anhydrous proton conductivity.

    19. Organometallic mediated radical polymerization of vinyl acetate with Fe(acac)2 (pages 3494–3504)

      Zhigang Xue and Rinaldo Poli

      Article first published online: 3 JUN 2013 | DOI: 10.1002/pola.26751

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      Poly(vinyl acetate) (PVAc) with controlled molecular weight and low dispersity is obtained by iron(II) acetylacetonate (Fe(acac)2)-mediated organometallic mediated radical polymerization. Isolation and characterization of a PVAc-FeIII(acac)2 oligomer and chain extension demonstrates the polymerization mechanism, but the controllability is limited by a relatively slow radical trapping rate.

    20. Solution processable polyamides containing thiazole units and thioether linkages with high optical transparency, high refractive index, and low birefringence (pages 3505–3515)

      Ali Javadi, Abbas Shockravi, Mahmood Kamali, Atefeh Rafieimanesh and Ali M. Malek

      Article first published online: 29 MAY 2013 | DOI: 10.1002/pola.26752

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      A series of novel polyamides bearing thiazole units and thioether linkages are synthesized. These polymers not only exhibit good solubility and high thermal stability, but also show high optical transparency, high refractive indices, and low birefringence. Therefore, thiazole-containing polyamides can open new perspectives to develop advanced optical devices.

    21. Aldol-type group-transfer polymerization of silyl vinyl ethers using silyl perfluoroalkaneimides as nonmetal catalysts (pages 3516–3522)

      Takaya Moyori, Terunari Hayashi and Akinori Takasu

      Article first published online: 29 MAY 2013 | DOI: 10.1002/pola.26753

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      The catalytic activity of bis(nonafluorobutanesulfonyl)imide (Nf2NH), acting as a Brønsted acid, and its silylated imide, t-butyldimethylsilyl nonafluorobutanesulfonylimide (Nf2NTBDMS), acting as a Lewis acid, was investigated for aldol-type group-transfer polymerization (Aldol-GTP) of silyl vinyl ethers. Aldol-GTPs of t-butyldimethylsilyl vinyl ether (VOTBDMS) and triethylsilyl vinyl ether (VOTES) proceeded in dichloromethane at 0 °C with benzaldehyde as the initiator. When Nf2NTBDMS was used as the catalyst, poly(VOTBDMS) with molecular weight >16,000 was obtained. With VOTES as the monomer and Nf2NTBDMS as the catalyst, a poly(VOTES) with a syndiotactic tendency (mm:mr:rr = 21:30:49) was produced.

    22. Diethylphosphonate-containing benzoxazine compound as a thermally latent catalyst and a reactive property modifier for polybenzoxazine-based resins (pages 3523–3530)

      Liang-Kai Lin, Chuang-Shao Wu, Wen-Chiung Su and Ying-Ling Liu

      Article first published online: 6 JUN 2013 | DOI: 10.1002/pola.26754

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      A diethylphosphonate-containing benzoxazine compound has been prepared to be used as a multi-functional reaction agent for preparation of high-performance polybenzoxazine thermosetting resins. The phosphonate group shows the thermally latent catalytic effect and flame retardation, and the benzoxazine group causes the compound to be a reactive-type reagent.

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