Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 48 Issue 19

1 October 2010

Volume 48, Issue 19

Pages 4141–4373

  1. Articles

    1. Top of page
    2. Articles
    3. Rapid Communications
    4. Notes
    1. Amphiphilic polymer conetworks prepared by controlled radical polymerization using a nitroxide cross-linker (pages 4141–4149)

      Weijie Zhao, Ming Fang, Junpo He, Junyu Chen, Wei Tang and Yuliang Yang

      Version of Record online: 24 AUG 2010 | DOI: 10.1002/pola.24156

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      Tandem ATRP and NMRP are used to synthesize amphiphilic conetworks with well-defined structures, using a bifunctional alkoxyamine possessing two acrylate units (di-AET). The swelling ability of the resulting conetwork, poly(styrene-co-acrylic acid), can be easily controlled by changing the cross-linking degree or the length of the PS segments.

    2. Combination of radical and cationic photoprocesses for the single-step synthesis of organic-inorganic hybrid films (pages 4150–4158)

      Cindy Belon, Abraham Chemtob, Céline Croutxé-Barghorn, Séverinne Rigolet, Vincent Le Houérou and Christian Gauthier

      Version of Record online: 24 AUG 2010 | DOI: 10.1002/pola.24182

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      In this work, the dual organic-–inorganic UV-curing of (meth)acrylate trimethoxysilane precursors is performed in one step through the association of a radical and a cationic photoinitiator. The interdependency between the acrylate polymerization and the photoinduced sol-–gel process is kinetically investigated by FTIR. In addition to the nano-organization study with X-ray diffraction, the mechanical property profiles of the resulting hybrid films are characterized upon combining scratch resistance and nanoindentation analysis.

    3. Poly(propylene glycol)-based ammonium ionenes as segmented ion-containing block copolymers (pages 4159–4167)

      Mana Tamami, Sharlene R. Williams, Jong Keun Park, Robert B. Moore and Timothy E. Long

      Version of Record online: 24 AUG 2010 | DOI: 10.1002/pola.24186

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      Segmented poly(propylene glycol) (PPG)-based ammonium ionenes were prepared via the Menschutkin reaction from bromine end-capped PPG oligomers and N,N,N′,N′-tetramethyl-1,6-hexanediamine. In addition, higher hard segment content ammonium ionenes were prepared by adding 1,12-dibromododecane as a third monomer. The effects of soft segment molecular weight and hard segment (HS) content on thermal, mechanical, and morphological behavior of PPG-based ammonium ionenes were investigated. Small angle X-ray scattering, atomic force microscopy and dynamic mechanical analysis confirmed the microphase separation of PPG-ionenes.

    4. Synthesis of cationic diacetylene-co-carbazole-co-fluorene polymers and their sensitive fluorescent quenching properties with DNA (pages 4168–4177)

      Wennan Zeng, Shouping Liu, Hanxun Zou, Linyun Wang, Roger Beuerman and Derong Cao

      Version of Record online: 24 AUG 2010 | DOI: 10.1002/pola.24197

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      Cationic conjugated polymers CPFC and CPF2C based on fluorenyl, diacetylene and carbazolyl units were synthesized. The polymers might be applied for the sensitive detection of CT DNA due to the fact that only minute addition of CT DNA (3.3 × 10−13 M) to the polymer solution could lead a distinct fluorescent quenching.

    5. Allyl sulfonium salt as a novel initiator for active cationic polymerization of epoxide by shooting with radicals species (pages 4178–4183)

      Faruk Yilmaz, Atsushi Sudo and Takeshi Endo

      Version of Record online: 24 AUG 2010 | DOI: 10.1002/pola.24198

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      Rapid cationic polymerization of cyclohexene oxide (CHO) was achived by combining the redox radical generation and the radical-to-acid converting system. Allylic sulfonium salt was used as a transforming reagent from free radicals into a highly efficient cationic initiator, tetrahydrothiophene-HX complex. Substituent (Y) at the allylic moiety and counter-ion (X) effects on the polymerization rate of CHO were also investigated.

    6. Noncovalent functionalization of multiwalled carbon nanotubes using graft copolymer with naphthalene and its application as a reinforcing filler for poly(styrene-co-acrylonitrile) (pages 4184–4191)

      Kyung Tae Kim and Won Ho Jo

      Version of Record online: 24 AUG 2010 | DOI: 10.1002/pola.24199

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      The graft copolymer-type compatibilizer, PVBEN-g-PMMA, for non-covalent functionalization of MWCNTs was synthesized, and the effect of the compatibilizer on the mechanical and electrical properties of SAN/MWCNT composites was examined.

    7. Poly(arylene thioether)s containing 9,9′-spirobifluorene moieties in the main chain: Masked dithiol-based synthesis and excellent optical properties (pages 4192–4199)

      Hitoshi Okuda, Ryota Seto, Yasuhito Koyama and Toshikazu Takata

      Version of Record online: 24 AUG 2010 | DOI: 10.1002/pola.24202

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      9,9′-Spirobifluorene-containing poly(arylene thioether)s (PTEs) were synthesized by the polycondensation of masked 2,2′-dithiol type monomer and difluoroarenes. They exhibited quite high refractive indices ranging from 1.69 to 1.73 at 587.6 nm, whereas little birefringence was observed due to C2-symmetric structure of spirobifluorene skeleton.

    8. Copolymerization of ethylene with isoprene promoted by titanium complexes containing a tetradentate [OSSO]-type bis(phenolato) ligand (pages 4200–4206)

      Carmine Capacchione, Daniela Saviello, Antonietta Avagliano and Antonio Proto

      Version of Record online: 24 AUG 2010 | DOI: 10.1002/pola.24204

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      Copolymerization of ethylene with isoprene catalyzed by 1,4-dithabutanediyl-linked bis(phenolato)titanium complexes 1 and 2 and methylaluminoxane (MAO) produced exclusively ethylene-isoprene copolymers with good activity. The copolymer microstructure can be varied by changing the ratio between the monomers in the copolymerization feed, affording copolymers with isoprene content up to 60%. The copolymer microstructure was fully elucidated by 13C NMR spectroscopy of the copolymers with various isoprene content revealing a strong tendency to the alternating microstructure.

    9. “Click polyester”: Synthesis of polyesters containing triazole units in the main chain via safe and rapid “click” chemistry and their properties (pages 4207–4218)

      Yu Nagao and Akinori Takasu

      Version of Record online: 24 AUG 2010 | DOI: 10.1002/pola.24206

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      Click Cu(I)-catalyzed polymerizations of diynes that contained ester linkages and diazides were performed to produce polyesters (click polyesters) of large molecular weights [(∼1.0–7.0) × 104], that contained main-chain 1,4-disubstitued triazoles in excellent yields. Incorporation of triazole improved the thermal properties and magnified the even-odd effect of the methylene chain length. We also found that, by changing the positions of the triazole rings, the thermal properties of the polyesters could be controlled. The use of in-situ azidation was a safe reaction, as explosive diazides are not used. In addition, microwave heating were found to accelerate the polymerization rates.

    10. Ethylene polymerization reactions with multicenter Ziegler-Natta catalysts—Manipulation of active center distribution (pages 4219–4229)

      Yury V. Kissin and Robert I. Mink

      Version of Record online: 24 AUG 2010 | DOI: 10.1002/pola.24208

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      This article describes ethylene/1-hexene copolymerization reactions with a supported multicenter Ziegler-Natta catalyst. The catalyst was modified by pretreating its solid precursor with organoaluminum chlorides, AlEt2Cl, Al2Et3Cl3, AlEtCl2, and AlMe2Cl. Analysis of the molecular weight distribution and compositional nonuniformity of copolymers prepared with the untreated and the modified catalysts demonstrated that the modification affects different types of active centers in the catalyst to a different degree.

    11. Copoly(peryleneimide)s containing 1,3,4-oxadiazole rings: Synthesis and properties (pages 4230–4242)

      Radu-Dan Rusu, Mariana-Dana Damaceanu, Luminita Marin and Maria Bruma

      Version of Record online: 24 AUG 2010 | DOI: 10.1002/pola.24209

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      Organosoluble, highly thermostable and processable into thin films and coatings copoly(peryleneimide)s were obtained by high temperature polycondensation reactions. The films are homogeneous, smooth and are self-organized into vertically segregated structures, due to π[BOND]π stacking interactions of perylenediimide units. The semicrystalline structure of the polymers consists in columns of perylene units arranged face-to-face, with different orientations and without intercolumnar correlations. The ether linkages in the polymer backbones induce excitation energy transfer from oxadiazole to perylenediimide moieties so that the photoluminescence spectra consist only of the emission of perylenediimide chromophore and conjugated segments with imide rings.

    12. The cyanine dye/trichloromethyl-1,3,5-triazine/thiols in two- and three-component photoinitiating systems for free radical polymerization (pages 4243–4251)

      Janina Kabatc

      Version of Record online: 24 AUG 2010 | DOI: 10.1002/pola.24210

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      The efficiency of the visible light induced polymerization of multifunctional acrylate in the presence of two- and three-component photoinitiating systems based of cyanine dye and heteroaromatic thiol or 1,3,5-triazine derivative was ascertained. The reaction mechanism by which active radical centers are produced by the three-component system comprised of cyanine dye, thiol, and 1,3,5-triazine derivative was proposed. This mechanism involves both, electron transfer from thiol to the dye and the electron transfer from dye to 1,3,5-triazine derivative, as the primary photochemical reactions. Thiol is an electron donor, reducing dye but 1,3,5-triazine derivative is an electron acceptor, acting to oxidize the excited dye. These reactions generate free radicals, which can serve as initiating radicals.

    13. Multistimuli-responsive hyperbranched poly(ether amine)s (pages 4252–4261)

      Bing Yu, Xuesong Jiang, Guilin Yin and Jie Yin

      Version of Record online: 24 AUG 2010 | DOI: 10.1002/pola.24211

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      Multistimuli-responsive hyperbranched poly(ether amine)s (hPEAs) were successfully prepared through one-pot synthesis. The obtained hPEAs can form the uniform-sized micelles, whose aggregation is sensitive to temperature, pH and ionic strength with the tunable CP.

    14. Covalent bonded polymer–graphene nanocomposites (pages 4262–4267)

      K. P. Pramoda, H. Hussain, H.M. Koh, H. R. Tan and C. B. He

      Version of Record online: 24 AUG 2010 | DOI: 10.1002/pola.24212

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      Octadecylamine functionalized graphite oxides are reacted with methacryloyl chloride to incorporate polymerizable [BOND]C[DOUBLE BOND]C[BOND] functionality at the nanographene platelet surfaces, which were subsequently employed in in situ polymerization of methylmethacrylate to obtain covalently bonded poly(methyl methacrylate) (PMMA)-graphene nanocomposites. The obtained nanocomposites show significant enhancement in thermal and mechanical properties compared to neat PMMA. Thus, even with 0.5 wt% graphene nanosheets, the Tg increased from 119 °C for neat PMMA to 131 °C for PMMA-graphene nanocomposite and the respective storage modulus increased from 1.29 GPa to 2 GPa.

    15. Thermo-responsive fluorescent micelles from amphiphilic A3B miktoarm star copolymers prepared via a combination of SET-LRP and RAFT polymerization (pages 4268–4278)

      Weidong Zhang, Wei Zhang, Zhengbiao Zhang, Zhenping Cheng, Yingfeng Tu, Yansheng Qiu and Xiulin Zhu

      Version of Record online: 24 AUG 2010 | DOI: 10.1002/pola.24214

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      The novel amphiphilic A3B miktoarm star copolymer poly(N-isopropylacrylamide)3-poly(N-vinylcarbazole) ((PNIPAAM)3(PVK)) was successfully prepared via a combination of SET-LRP and RAFT techniques. The fluorescent micelle from self-assembly of (PNIPAAM)3(PVK) are responsive to the temperature, which made it well suited for potential applications as sensitive probe for the microscopic environmental change.

    16. Benzoxazine containing polyester thermosets with improved adhesion and flexibility (pages 4279–4284)

      Alev Tuzun, Baris Kiskan, Neslihan Alemdar, A. Tuncer Erciyes and Yusuf Yagci

      Version of Record online: 24 AUG 2010 | DOI: 10.1002/pola.24215

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      High molecular weight polyesters containing thermally curable benzoxazine units in the main chain have been synthesized. For this purpose, first the diol functional monomer is synthesized through the Mannich and subsequent ring closure reactions of bisphenol-A, paraformaldehyde, and 5-amino-1-pentanol. Polycondensation of the resulting benzoxazine and pyromellitic dianhydride or 4-4′-(hexafluroisoproplylidene) diphatalic anhydride with or without dibutyltin laurate yielded the corresponding polyesters with the molecular weights between 5800 and 7000 Da.

    17. Bioengineering functional copolymers. XV. Synthesis and characterization of poly(N-isopropyl acrylamide-co-3,4-dihydro-2H-pyran-alt-maleic anhydride)s and their PEO branched derivatives (pages 4285–4295)

      Zakir M. O. Rzayev, Mustafa Türk and Ayşe Uzgören

      Version of Record online: 24 AUG 2010 | DOI: 10.1002/pola.24217

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      Novel bioengineering functional terpolymers with supramacromolecular structure and controllable hydrophilic/hydrophobic interaction were synthesized by complex-radical terpolymerization of N-isopropyl acrylamide, 3,4-dihydro-2H-pyran and maleic anhydride. Investigation into the factors affecting the antitumor activity revealed that terpolymers containing a combination of H-bonded ionizable amide and carboxylic groups exhibited reversible coil-globule transition behavior and higher cytotoxity towards SCLC cancer cells.

    18. Molecular weight and configurational stability of poly[(fluorophenyl)acetylene]s prepared with metathesis and insertion catalysts (pages 4296–4309)

      Dmitrij Bondarev, Jiří Zedník, Iva Plutnarová, Jiří Vohlídal and Jan Sedláček

      Version of Record online: 24 AUG 2010 | DOI: 10.1002/pola.24218

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      High-cis and cis/trans poly[(fluorophenyl)acetylene]s with F substituent in 2, 3, and 4positions on Ph ring have been prepared and studied as to their molecular weight and configurational stability in air. Effects of fluorine position, main-chain configuration, and ageing conditions on the stability are discussed. When aged in the solid- state, polymers underwent slow degradation. The rate of degradation increased up to three orders of magnitude in THF where it was lower for cis/trans compared with high-cis samples probably because of simultaneously proceeding cis-to-trans isomerization. Hypothesis was postulated on the interconnection of degradation and cis-to-trans isomerization.

    19. Hybrid organo-inorganic globular nanospecies: Transition from macromolecule to particle (pages 4310–4322)

      N. V. Voronina, I. B. Meshkov, V. D. Myakushev, T. V. Laptinskaya, V. S. Papkov, M. I. Buzin, M. N. Il'ina, A. N. Ozerin and A. M. Muzafarov

      Version of Record online: 24 AUG 2010 | DOI: 10.1002/pola.24219

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      Hybrid nanoparticles “inorganic core - organic shell” were prepared from different silica-precursors (hyperbranched polyethoxysiloxane, silicasol and tetraethoxysiloxane). In all cases a qualitative “macromolecule - particle” transition was found as the “core - shell” mass ratio increases. This transition was accompanied by the increase of molecular masses and Tg of hybrid nanoparticles. The particles obtained were studied by GPC, DLS, viscometry, thermomechanics, WAXS. This work might shed some lights on the use of core-shell systems for the preparation of nanocomposites.

    20. Synthesis and characterization of novel methacrylate copolymers based on sulfonamide and coumarine: Monomer reactivity ratios, biological activity, thermal stability, and optical properties (pages 4323–4334)

      Ibrahim Erol, Gülay Sanli, Meltem Dİlek and Levent Ozcan

      Version of Record online: 24 AUG 2010 | DOI: 10.1002/pola.24220

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      The synthesis of new methacrylate monomers (SAEMA) having pendant sulfonamide and MCMA having pendant coumarine moieties have been reported for the first time. The structure of monomers and their homopolymers were characterized by spectroscopic methods. Copolymers of this monomers and different copolymer compositions were prepared. The reactivity ratio values were derived from the F-R and K-T methods were in good agreement with each other. The biological activity and thermal stability of the polymers were investigated. The decomposition activation energies of the polymers were calculated with the Ozawa method. The photochemical properties of the polymers were investigated by UV spectra.

    21. Hydrophilic functionalization of syndiotactic polystyrene via a combination of electrophilic bromination and Suzuki–Miyaura reaction (pages 4335–4343)

      Jihoon Shin, Ying Chang, Thi Le Thanh Nguyen, Seok Kyun Noh and Chulsung Bae

      Version of Record online: 24 AUG 2010 | DOI: 10.1002/pola.24222

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      Functionalization of syndiotactic polystyrene was achieved via combination of electrophilic bromination at the para-position of the polymer aromatic ring and subsequent Suzuki–Miyaura cross-coupling reactions with functionalized phenylboronic acids. The concentration of functional group in polystyrene repeating unit was conveniently controlled by changing the ratio of added bromine relative to the polymer repeating unit. Improvement in surface properties of functionalized polymer was confirmed by measuring water contact angles.

  2. Rapid Communications

    1. Top of page
    2. Articles
    3. Rapid Communications
    4. Notes
    1. You have free access to this content
      Incorporation of ketone groups into poly(4-hydroxystyrene)s main chain by radical copolymerization of 4-(tert-butoxy)styrene and 2,2-diphenyl-4-methylene-1,3-dioxolane and their photoscission (pages 4344–4350)

      Takeshi Ishikawa, Kazuhide Morino, Atsushi Sudo and Takeshi Endo

      Version of Record online: 24 AUG 2010 | DOI: 10.1002/pola.24200

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      Poly(4-hydroxystyrene)s having ketone groups in the main chain were synthesized by the radical copolymerization of 2,2-diphenyl-4-methylene-1,3-dioxolane (DPMD) with 4-tert-butoxystyrene (tBOSt) followed by the removal of the tert-butyl groups of the obtained copolymers. The obtained copolymers showed good photodegradability.

    2. You have free access to this content
      Revolutionary phosgene-free synthesis of α-amino acid N-carboxyanhydrides using diphenyl carbonate based on activation of α-amino acids by converting into imidazolium salts (pages 4351–4355)

      Koichi Koga, Atsushi Sudo and Takeshi Endo

      Version of Record online: 24 AUG 2010 | DOI: 10.1002/pola.24213

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      α-Amino acids imidazolium salt smoothly reacted with diphenylcarbonate to afford the corresponding urethanes. The urethanes were activated by adding carboxylic acid to undergo selective cyclization, leading to successful development of a new phosgene-free process for synthesizing α-amino acid N-carboxyanhydrides (NCAs).

    3. You have free access to this content
      High internal phase emulsions prepared with poly(urethane urea) aqueous nanodispersion at different temperatures (pages 4356–4360)

      Yun Zhu, Shengmiao Zhang, Jianding Chen and Chun Pu Hu

      Version of Record online: 24 AUG 2010 | DOI: 10.1002/pola.24221

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      Pickering emulsions having internal phase of up to 93.3 vol % were prepared with PUU aqueous nanodispersion as the aqueous phase. And porous polymers based on the Pickering HIPEs were obtained. The void walls were populated by particles which were also at the interface.

    4. You have free access to this content
      Synthesis of a cellulose supported chain transfer agent and its application to RAFT polymerization (pages 4361–4365)

      Mona Semsarilar, Vincent Ladmiral and Sébastien Perrier

      Version of Record online: 24 AUG 2010 | DOI: 10.1002/pola.24232

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      A new route for the homogeneous synthesis of cellulose-based RAFT agents is proposed. The resulting cellulose-supported RAFT agent is used to mediate the polymerization of N-isopropyl acrylamide (NIPAAm), and yields cellulose-graft-Poly(NIPAAm).

    5. You have free access to this content
      Novel direct synthetic approach to thiol-functionalized poly(ε-caprolactone) by highly chemselective and low costly rare earth phenolate catalysts (pages 4366–4369)

      Ning Zhu, Jun Ling, Yinghong Zhu, Weilin Sun and Zhiquan Shen

      Version of Record online: 24 AUG 2010 | DOI: 10.1002/pola.24233

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      Highly chemselective and low costly rare earth phenolate catalysts for direct synthesis of thiol-functionalized poly(ε-caprolactone) (PCLSH) has been developed. Well-defined PCLSH polymers are obtained without tedious protecting/deprotecting steps via this convenient synthetic approach.

  3. Notes

    1. Top of page
    2. Articles
    3. Rapid Communications
    4. Notes
    1. You have free access to this content
      Two-step thermochromism in poly(3-docosoxy-4-methylthiophene): Mechanistic similarity to poly(3-docosylthiophene) (pages 4370–4373)

      Dinesh Chalasani, Joshua K. Potvin, Brett L. Lucht and William B. Euler

      Version of Record online: 24 AUG 2010 | DOI: 10.1002/pola.24236

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      Poly(3-docosoxy-4-methylthiophene) (PDMT) was synthesized and investigated. PDMT can form a mesophase by rapid quenching from the isotropic melt. Variable- temperature reflection and fluorescence spectroscopy of thin films and differential scanning calorimetry were used to study the thermal behavior of PDMT. PDMT shows a two- step thermochromic transition from the mesophase, and endotherms in the thermograms could be assigned to melting of each phase. A comparison to with related poly(3-alkylthiophene)s suggests that the mechanism of the thermochromic transition is very similar.