Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 45 Issue 20

15 October 2007

Volume 45, Issue 20

Pages 4545–4750

  1. Articles

    1. Top of page
    2. Articles
    1. A Diels-Alder/retro Diels-Alder strategy to synthesize polymers bearing maleimide side chains (pages 4545–4551)

      Tugba Dispinar, Rana Sanyal and Amitav Sanyal

      Version of Record online: 4 SEP 2007 | DOI: 10.1002/pola.22299

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      Polymers containing thiol-reactive maleimide groups in their side chains have been synthesized by utilization of a novel acrylate monomer containing a masked maleimide. Diels-Alder reaction between furan and maleimide was adapted for the protection of the reactive maleimide double bond prior to polymerization. After free radical polymerization, the maleimide groups in the side chain of the polymer were unmasked into their reactive form by utilization of retro Diels-Alder reaction. [Color figure can be viewed in the online issue, which is available at www.interscience.]

    2. Tailored surface properties of monodispersed polymer particles with PCL hairy chains synthesized by hydroxyl-initiated ring-opening polymerization (pages 4552–4563)

      Fang Wang, Jianhua Hu, Wuli Yang and Changchun Wang

      Version of Record online: 29 AUG 2007 | DOI: 10.1002/pola.22161

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      Polymeric particles with hydrophobic PCL hairy chains were prepared by ring-opening polymerization from hydrophilic core particles, which were prepared by soap-free emulsion polymerization of styrene, 2-hydroxyethyl methacrylate, and divinylbenzene. The presence of hydrophobic polymeric hairs on the surface of the particles has led to dramatic improvement in their dispersibility in oil phase. The grafting amount of PCL could be well characterized by thermogravimetric analysis. [Color figure can be viewed in the online issue, which is available at]

    3. Synthesis and characterization of liquid crystalline side-chain block copolymers containing luminescent 4,4′-bis(biphenyl)fluorene pendants (pages 4564–4572)

      Kuan-Wei Lee and Hong-Cheu Lin

      Version of Record online: 29 AUG 2007 | DOI: 10.1002/pola.22167

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      A series of new liquid crystalline homopolymers, copolymers, and block copolymers were polymerized from styrene-macroinitiator (SMi) and methacrylates with pendent 4,4′-bis(biphenyl)fluorene (M1) and biphenyl-4-ylfluorene (M2) groups through atom transfer radical polymerization (ATRP). The thermal, mesogenic, and photoluminescent (PL) properties of all polymers were investigated.

    4. Poly(arylate-phosphonate) copolymers with deoxybenzoin in the backbone: Synthesis, characterization, and thermal properties (pages 4573–4580)

      T. Ranganathan, Bon-Cheol Ku, Joseph Zilberman, Michael Beaulieu, Richard J. Farris, E. Bryan Coughlin and Todd Emrick

      Version of Record online: 29 AUG 2007 | DOI: 10.1002/pola.22188

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      Deoxybenzoin-based copolymers containing various ratios of arylate and phenylphosphonate units in the backbone were synthesized by solution polycondensation. Integration of phosphonate units into the polymer backbone is advantageous for achieving high molecular weight polymers with solution processibility. These copolymers showed extremely low heat release capacity (40–60 J/g K) and very high char yields (52–58%), making them attractive for applications in which halogen-free, low flammability materials are desired.

    5. Homo- and copolymerization of norbornene derivatives with ethene by ansa-fluorenylamidodimethyltitanium activated with methylaluminoxane (pages 4581–4587)

      Tariqul Hasan, Tomiki Ikeda and Takeshi Shiono

      Version of Record online: 29 AUG 2007 | DOI: 10.1002/pola.22193

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      ansa-Fluorenylamidodimethyltitanium (1) activated with MAO conducted copolymerization of ethene with 5-ethylidene-2-norbornene (5E2N), and terpolymerization of ethene with 5E2N and norbornene (N) in high activity to give the random co- and terpolymers. The glass transition temperatures and the 5E2N contents of the products were controlled by the ethene/ (N + 5E2N) ratio and the 5E2N/ (ethene + N) ratio, respectively, in a wide range.

    6. Synthesis of silicon-bridged polythiophene derivatives and their applications to EL device materials (pages 4588–4596)

      Joji Ohshita, Keisuke Kimura, Kwang-Hoi Lee, Atsutaka Kunai, Young-Woo Kwak, Eun-Chul Son and Yoshihito Kunugi

      Version of Record online: 4 SEP 2007 | DOI: 10.1002/pola.22196

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      Oxidative homo-coupling of 2,6-bis(tributylstannyl)dithienosiloles afforded poly(dithienosilole-2,6-diyl)s as novel polythiophene derivatives with intra-chain silicon bridges, which exhibited red-shifted UV absorption maxima, as compared with those of silole-free polythiophenes. Alternate copolymers also were prepared by cross-coupling reactions of 2,6-dibromodithienosiloles with distannylthiophene or bithophene. Applications of the resulting polymers to electroluminescence devices and a field effect transistor were also studied.

    7. Radical copolymerization of alkyl 2-norbornene-2-carboxylate with alkyl acrylates: Facile incorporation of norbornane framework into poly(alkyl acrylate)s (pages 4597–4605)

      Eiji Ihara, Shingo Honjyo, Tomomichi Itoh, Kenzo Inoue and Mitsufumi Nodono

      Version of Record online: 11 SEP 2007 | DOI: 10.1002/pola.22197

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      Radical copolymerization of alkyl 2-norbornene-2-carboxylates (alkyl = Me 1a, nBu 1b) with alkyl acrylates (alkyl =ethyl, methyl, and n-butyl) was investigated. Copolymerization of 1a,b with the alkyl acrylates initiated by 1,1′-azobis(cyclohexane-1-carbonitrile) at 85 °C proceeded to give random copolymers, although the homopolymerization of 1a,b did not proceed efficiently under the same conditions. An increase of Tg derived from the incorporation of the rigid norbornane framework was observed although the extent of the temperature rise was rather moderate. The ternary radical copolymerization of 1a,b/alkyl acrylate/N-phenylmaleimide proceeded to give copolymers with the three repeating units in the main chain.

    8. Acceleration effect of five-membered cyclic dithiocarbonate on an epoxy–amine curing system (pages 4606–4611)

      Masashi Horikiri, Atsushi Sudo and Takeshi Endo

      Version of Record online: 29 AUG 2007 | DOI: 10.1002/pola.22198

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      The addition of a five-membered cyclic dithiocarbonate (DTC) to an epoxy–amine curing system resulted in a remarkable reduction of the time for evolution of storage modulus. Detailed studies on the corresponding model reactions revealed that the thiourethane moiety formed by the ring-opening reaction of DTC with amine proved remarkably effective in promoting the addition reaction of epoxide and amine.

    9. Synthesis and characterization of spherical and hemispherical polyepoxide micrometer-sized particles of narrow size distribution by a single-step swelling of uniform polystyrene template microspheres with glycidyl methacrylate (pages 4612–4622)

      Melany Omer-Mizrahi and Shlomo Margel

      Version of Record online: 29 AUG 2007 | DOI: 10.1002/pola.22199

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      Uniform polystyrene/poly(glycidyl methacylate-ethylene glycol dimethacrylate) polyepoxide composite microspheres were synthesized by a single-step swelling of the polystyrene template microspheres with the swelling solvent monomers glycidyl methacylate and ethylene glycol dimethacrylate, followed by polymerization of the monomers within the swollen template microspheres at 73 °C.

    10. Branched poly(styrene-b-tert-butyl acrylate) and poly(styrene-b-acrylic acid) by ATRP from a dendritic poly(propylene imine)(NH2)64 core (pages 4623–4634)

      Young Hie Kim, Warren T. Ford and Thomas H. Mourey

      Version of Record online: 7 SEP 2007 | DOI: 10.1002/pola.22200

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      The primary amine end groups of poly(propylene imine) dendrimer DAB-dendr-(NH2)64 were converted to 2-bromoisobutyramide groups for initiation of ATRP, and blocks of polystyrene and poly(tert-butyl acrylate) were grown. The tert-butyl groups were removed to produce poly(styrene-b-acrylic acid). SEC absolute molecular weight analyses of the PS-b-PtBA indicated many fewer branches than the number of initiator groups on the dendrimer. The PS-b-PAA dissolved molecularly in DMF and formed aggregates in water. AFM images of the aggregates showed discs and worm-like rods similar to those observed with linear PS-b-PAA.

    11. Butadiene–isoprene copolymerization with V(acac)3-MAO. Crystalline and amorphous trans-1,4 copolymers (pages 4635–4646)

      Giovanni Ricci, Lucia Zetta, Enrica Alberti, Tiziano Motta, Maurizio Canetti and Fabio Bertini

      Version of Record online: 4 SEP 2007 | DOI: 10.1002/pola.22209

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      Copolymerization of butadiene with isoprene, catalyzed by V(acac)3-MAO, gives exclusively trans-1,4 copolymers with high activity. The two comonomers are statistically distributed along the polymer chain, and the copolymers are crystalline or amorphous depending on the isoprene content. Copolymer microstructure, comonomer composition and distribution along the polymer chain were fully elucidated by 13C and 1H NMR spectroscopy; the thermal and X-ray behaviors of the copolymers were also investigated.

    12. Conducting and magnetic behaviors of monodispersed iron oxide/polypyrrole nanocomposites synthesized by in situ chemical oxidative polymerization (pages 4647–4655)

      Tzong-Ming Wu, Shiang-Jie Yen, Erh-Chiang Chen, Ti-Wen Sung and Ray-Kuang Chiang

      Version of Record online: 4 SEP 2007 | DOI: 10.1002/pola.22211

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      Monodispersed 4 nm Fe3O4 nanoparticles used as a core in the formation of tubular shells of the Fe3O4/PPy nanocomposites were successfully synthesized via in situ polymerization. Morphology of the nanocomposites shows a remarkable change from spherical to tube-like structures as the content of monodispersed Fe3O4 nanoparticles increases from 9% to 24 wt %. The conductivities of these Fe3O4/PPy nanocomposites are about six times higher than those of PPy without Fe3O4. The magnetic properties of 24 wt % and 36 wt % PPy/Fe3O4 nanocomposites show ferromagnetic behavior and supermagnetism, respectively.

    13. Chapman rearrangement in the synthesis of aromatic polyamides (pages 4656–4660)

      V. F. Burdukovskiy, D. M. Mognonov and I. A. Farion

      Version of Record online: 4 SEP 2007 | DOI: 10.1002/pola.22212

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      The article describes synthesis of N-substituted aromatic polyamides via Chapmen's rearrangement of polyiminoesters. The polyamides obtained possess high thermal stability, good solubility in common organic solvents, and film-forming properties.

    14. Alternating copolyfluorenevinyles with polynuclear aromatic moieties: Synthesis, photophysics, and electroluminescence (pages 4661–4670)

      John A. Mikroyannidis, Larysa Fenenko, Masayuki Yahiro and Chihaya Adachi

      Version of Record online: 4 SEP 2007 | DOI: 10.1002/pola.22213

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      Soluble copolyfluorenevinylenes N, A, and P were synthesized by Heck coupling. Their glass transition temperatures increased by increasing the number of the phenyl rings of the polynuclear aromatic moiety. Although the copolymers showed high-efficiency blue (N) and blue-greenish (A and P) fluorescence in their 10−6 M THF solution, significant decreases of PL efficiency were observed in their films, indicating the presence of concentration quenching in their solid state films. The OLEDs showed EL with ηEL = 0.26–0.31%, green in the case of N and A, and red in the P. The polymers N, A, and P are candidates for optoelectronic applications.

    15. Effect of pendent oxyethylene moieties on the properties of aromatic polyisophthalamides (pages 4671–4683)

      Juan J. Ferreiro, José G. de la Campa, Angel E. Lozano, Javier de Abajo and Jack Preston

      Version of Record online: 5 SEP 2007 | DOI: 10.1002/pola.22214

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      Polyisophthalamides containing short sequences of oxyethylene as pendent substituents were synthesized by the reaction of technical diamines and four novel diacid monomers containing pendent oxyethylene units. The polymers were prepared in high yield and high molecular weight by the phosphorylation method of polycondensation. All of the polymers were soluble in organic aprotic solvents and showed good mechanical properties. However, the presence of the oxyethylene side sequences substantially lowered the thermal resistance and the glass transition temperatures. A study was also made on the effect of the chemical composition on water uptake.

    16. Synthesis of perfectly bifunctional polyacrylates by single-electron-transfer living radical polymerization (pages 4684–4695)

      Gerard Lligadas and Virgil Percec

      Version of Record online: 7 SEP 2007 | DOI: 10.1002/pola.22307

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      Poly(methyl acrylate)s, poly(ethyl acrylate)s, and poly(butyl acrylate)s with α,ω-di(bromo) chain ends and Mn from 8500 to 35,000 were synthesized by SET-LRP. The analysis of their chain ends by a combination of methods consisting of 1H and 2D-NMR, GPC, MALDI-TOF MS, chain end functionalization, chain extension, and halogen exchange experiments demonstrated the synthesis of perfectly bifunctional α,ω-di(bromo)polyacrylates.

    17. Synthesis and characterization of star polyfluorenes with a C60 core (pages 4696–4706)

      Guodong Xu, Yang Han, Minghao Sun, Zhishan Bo and Chunhai Chen

      Version of Record online: 7 SEP 2007 | DOI: 10.1002/pola.22215

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      A high yield hexakisaddition of C60 was developed by using Prato reaction and bulky fluorene addends. Suzuki polycondensation of the obtained hexakisadducts of C60 and AB-type fluorene monomer with Pd(PPh3)4 as the catalyst precursor afforded the desired C60-cored star polyfluorenes. Their three-dimensional structure can effectively reduce the aggregation of the polyfluorene chains. Annealing studies indicated that C60-cored star polyfluorenes are of good color stability.

    18. Synthesis and properties of new fluorinated ester, thioester, and amide substituted polythiophenes. Towards superhydrophobic surfaces (pages 4707–4719)

      Mael Nicolas, Frédéric Guittard and Serge Géribaldi

      Version of Record online: 7 SEP 2007 | DOI: 10.1002/pola.22216

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      A series of new fluorinated polythiophenes has been synthesized by oxidative chemical and electrochemical polymerization and by Ullmann coupling, the perfluoroalkyl alkyl chain being covalently bounded, before polymerization, to monomer via an ester, thioester, or amide connector. The role of the linker was analyzed on the efficiency of the polymerization reactions and on the properties of the corresponding polymers. With an ester group, the Ullmann coupling furnishes fluorinated soluble oligomers with a high electron affinity while the electropolymerization gives rise to porous fluorinated polymers that present stable superhydrophobicity.

    19. Polymerization and self-assembly of thermally responsive in-chain functionalized double-hydrophilic macromonomers (pages 4720–4732)

      Iliyana V. Berlinova, Plamen V. Iliev, Nikolay G. Vladimirov and Christo P. Novakov

      Version of Record online: 7 SEP 2007 | DOI: 10.1002/pola.22220

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      In-chain functionalized double-hydrophilic macromonomers were synthesized via interaction of poly(N-isopropylacrylamide) monoester of maleic acid with amino- or hydroxyl end-capped methoxy-poly(ethylene oxide). The polymerization performed in the organized domains from macromonomers in aqueous solutions at temperatures above and below their phase transition temperature (Ttr) afforded hetero-chain star-shaped and brush copolymers. They were inclined to form associates below the Ttr.

    20. Addition polymerization of norbornene using bis(β-ketoamino)nickel(II)/tris(pentafluorophenyl)borane catalytic systems (pages 4733–4743)

      Xiaohui He, Yiwang Chen, Yongming Liu, Shuxian Yu, Sanguo Hong and Qing Wu

      Version of Record online: 7 SEP 2007 | DOI: 10.1002/pola.22221

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      Norbornene polymerizations proceeded in toluene with bis(β-ketoamino)nickel(II) complexes as the catalyst precursors and the organo-Lewis compound tris(pentafluorophenyl)borane as a unique cocatalyst. Both bis(β-ketoamino)nickel(II)/tris(pentafluorophenyl)borane catalytic systems showed noticeably high conversions and activities. The achieved polynorbornenes were confirmed to be vinyl-addition and atactic polymers.

    21. Generation of core/shell iron oxide magnetic nanoparticles with polystyrene brushes by atom transfer radical polymerization (pages 4744–4750)

      I. Garcia, A. Tercjak, N. E. Zafeiropoulos, M. Stamm and I. Mondragon

      Version of Record online: 7 SEP 2007 | DOI: 10.1002/pola.22233

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      The surface of iron oxide magnetic nanoparticles was modified with atom transfer radical polymerization and a grafting-from approach. The modification was carried out with copper bromide and 2,2′-bipyridine as a catalyst system and with p-toluenesulfonyl chloride as a free initiator. After the polymerization, the magnetic nanoparticles had a graft density of 0.9 PS chains/nm2. Good control of the polymerization and a narrow polydispersity for the polymer brushes were obtained with the free initiator.