Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 45 Issue 18

15 September 2007

Volume 45, Issue 18

Pages 4185–4400

  1. Articles

    1. Top of page
    2. Articles
    3. Rapid Communications
    4. Notes
    1. Starch-graft-(synthetic copolymer) latexes initiated with Ce4+ and stabilized by amylopectin (pages 4185–4192)

      Hank De Bruyn, Ewan Sprong, Marianne Gaborieau, John A. Roper III and Robert G. Gilbert

      Version of Record online: 6 AUG 2007 | DOI: 10.1002/pola.22189

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      A method is presented for synthesizing surfactant-free latexes comprising starch-graft-(vinyl polymer) using Ce4+ to create grafting sites on the starch. Colloidally stable polystyrene, poly(styrene-co-n-butyl acrylate) and poly(vinyl acetate) latexes grafted onto high molecular weight amylopectin were developed. Furthermore, reaction rates of Ce4+ with simple sugars and polysaccharides were investigated, as well as gelation mechanism of the latex.

    2. Elaboration of open-cell microcellular nanocomposites (pages 4193–4203)

      O. Lépine, M. Birot and H. Deleuze

      Version of Record online: 26 JUL 2007 | DOI: 10.1002/pola.22160

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      Stable W/O high internal phase emulsions (HIPEs), containing styrene and divinylbenzene monomers and exfoliated montmorillonite, were prepared and copolymerized to obtain microcellular nanocomposite materials. The presence of modified clay did not alter the microcellular structure of the obtained polyHIPE but significantly enhanced its rigidity and yield strength.

    3. Self-assembly of amphiphilic tris(2,2′-bipyridine)ruthenium-cored star-shaped polymers (pages 4204–4210)

      Guangchang Zhou, Jibao He and Issifu I. Harruna

      Version of Record online: 6 AUG 2007 | DOI: 10.1002/pola.22163

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      The new amphiphilic star-shaped metallopolymers of polystyrene and poly(N-isopropylacrylamide) self-assembled in aqueous solutions into core-shell micelles in which the metal ions located on the core–shell interface. The micelle particle sizes varied with the hydrophilic poly(N-isopropylacrylamide) block length and sample concentration.

    4. Novel silicon-containing spiroorthoester to confer combined flame retardancy and low shrinkage properties to epoxy resins (pages 4211–4224)

      J. Canadell, A. Mantecón and V. Cádiz

      Version of Record online: 26 JUL 2007 | DOI: 10.1002/pola.22164

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      A new silicon-containing spiroorthoester, 1,4,6-trioxaspiro[4,4]-2-nonylmethyl 3-trimethylsilyl propionate (SOE[BOND]Si), was synthesized and confirmed its structure by 1H and 3C NMR. This SOE[BOND]Si and a mixture of DGEBA/SOE[BOND]Si were polymerized with ytterbium triflate. The curing was studied with differential scanning calorimetry and monitored by Fourier transform infrared spectroscopy. The materials were characterized with differential scanning calorimetry, termogravimetric analysis and thermodynamomechanical analysis. The volume change was evaluated with a Micromeritics gas pycnometer and the flame retardancy was tested by the limiting oxygen index measurements.

    5. Synthesis and characterization of tris(2,2′-bipyridine)ruthenium-cored star-shaped polymers via RAFT polymerization (pages 4225–4239)

      Guangchang Zhou, Jibao He and Issifu I. Harruna

      Version of Record online: 26 JUL 2007 | DOI: 10.1002/pola.22219

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      Bipyridine end-functionalized polystyrene and poly(N-isopropylacrylamide) polymers were prepared by RAFT polymerization using a new bipyridine-functionalized dithioester as a RAFT agent. The RAFT-prepared bipyridine-terminated polymers were further used as macroligands to complex with ruthenium ions to produce homogenous and amphiphilic star-shaped metallopolymers.

    6. Nucleobases modified azo-polysiloxanes, materials with potential application in biomolecules nanomanipulation (pages 4240–4248)

      Nicolae Hurduc, Ramona Enea, Dan Scutaru, Liviu Sacarescu, Bogdan C. Donose and Anh V. Nguyen

      Version of Record online: 31 JUL 2007 | DOI: 10.1002/pola.22165

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      Minimum energy chain conformation obtained by molecular simulation, corresponding to an azo-polysiloxane modified with adenine (single chain). This class of materials presents a potential interest in the field of molecules immobilization and nanomanipulation.

    7. Polycyclotrimerization of aromatic diynes: Synthesis, thermal stability, and light-emitting properties of hyperbranched polyarylenes (pages 4249–4263)

      Matthias Häußler, Jianzhao Liu, Jacky Wing Yip Lam, Anjun Qin, Ronghua Zheng and Ben Zhong Tang

      Version of Record online: 31 JUL 2007 | DOI: 10.1002/pola.22246

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      New aromatic diyne monomers are synthesized. Their homo- and copolymerizations are effected by transition-metal catalysts, yielding soluble hyperbranched polyarylenes with high molecular weights in high yields. The polymers show excellent thermal stability and carbonize in high yields when pyrolyzed at 900 °C. Upon photoexcitation, dichloromethane solutions of the polymers emit strong deep blue light of ∼ 400 nm with quantum yields up to 92%. [A color version of the adjacent figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    8. Nanocomposites through copolymerization of a polyhedral oligomeric silsesquioxane and methyl methacrylate (pages 4264–4275)

      Noa Amir, Anastasia Levina and Michael S. Silverstein

      Version of Record online: 31 JUL 2007 | DOI: 10.1002/pola.22168

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      The mechanical properties and thermal stability of polymers can be enhanced through the formation of nanocomposites. The formation of such nanocomposites through the synthesis of hybrid copolymers of methyl methacrylate (MMA) and a polyhedral oligomeric silsesquioxane (POSS) bearing one methacrylate group and seven cyclohexyl groups, and the structure and properties of the resulting copolymers, are described herewith. The schematic diagram illustrates the differences in the degradation processes between PMMA and the more thermally stable nanocomposite hybrid copolymer. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    9. Third-generation amphiphilic conetworks. III. Permeabilities and mechanical properties (pages 4276–4283)

      Jungmee Kang, Gabor Erdodi and Joseph P. Kennedy

      Version of Record online: 31 JUL 2007 | DOI: 10.1002/pola.22170

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      Continuum model of our amphiphilic conetwork: Glucose and insulin permeate through the aqueous phase, while oxygen diffuses through the hydrophobic domains. Because of the presence of the hydrophobic domains the network is strong, and the hydrophobic domains create tortuous channels. In this cocontinuous amphiphilic conetwork the perm-selectivity of glucose and insulin over antibodies is enhanced. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    10. Synthesis, characterization, and crosslinking of methacrylate-telechelic PDMAAm-b-PDMS-b-PDMAAm copolymers (pages 4284–4290)

      Radhakrishnan Karunakaran and Joseph P. Kennedy

      Version of Record online: 31 JUL 2007 | DOI: 10.1002/pola.22169

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      The synthesis and molecular characterization of a new amphiphilic conetwork (APCN) designed for silicone hydrogel use is described. The synthesis strategy, outlined in Scheme 1, calls for the preparation, by the RAFT technique, of a new methacrylate-telechelic amphiphilic pentablock, MA-PHEA-b-PDMAAM-b-PDMS-b-PDMAAm-b-PHEA-MA, and its crosslinking to the target APCN. The sketch shows the architecture of the APCN (dotted lines: PDMAAm, solid lines: PDMS; clusters: MA- based crosslinking sites). All six synthesis steps proceed smoothly and efficiently, and the products are optically clear colorless membranes exhibiting properties appropriate for ophthalmic use. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    11. Synthesis and characterization of novel poly(p-phenylenevinylene) derivatives containing phenothiazine-5-oxide and phenothiazine-5, 5-dioxide moieties (pages 4291–4299)

      L. Y. Yang, C. Wang, L. Q. Li, S. Janietz, A. Wedel, Y. L. Hua and S. G. Yin

      Version of Record online: 6 AUG 2007 | DOI: 10.1002/pola.22171

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      PPV-based copolymers containing phenothiazine-5-oxide and phenothiazine-5, 5-dioxide moieties have been synthesized by Wittig-Horner reaction and characterized by means of UV-vis, PL, EL spectra and cyclic voltammetry. The results of EL and electrochemical analyses revealed that they are promising candidate materials for organic, light-emitting diodes with hole-transporting ability.

    12. Well-controlled polymerization of 2-azidoethyl methacrylate at near room temperature and click functionalization (pages 4300–4308)

      Yu Li, Junwei Yang and Brian C. Benicewicz

      Version of Record online: 6 AUG 2007 | DOI: 10.1002/pola.22172

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      A “clickable” polymer was prepared by the near-room-temperature RAFT polymerization of 2-azidoethyl methacrylate, with excellent control over the molecular weight and molecular weight distribution at low-to-high conversions.

    13. Facile synthesis and characterization of hyperbranched poly(ether amide)s generated from Michael addition polymerization of in situ created AB2 monomers (pages 4309–4321)

      Ying Lin, Zhong-Ming Dong, Xiao-Hui Liu and Yue-Sheng Li

      Version of Record online: 3 AUG 2007 | DOI: 10.1002/pola.22175

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      A series of novel hyperbranched poly(ether amide)s was synthesized via Michael addition polymerization from in situ created AB2 monomers. The molecular weight, branched architecture, and unique solution property of the resultant hyperbranched polymers were thoroughly characterized.

    14. First solvent-free synthesis of poly(N-methylolacrylamide) via frontal free-radical polymerization (pages 4322–4330)

      Li Chen, Ting Hu, Huan Yu, Su Chen and John A. Pojman

      Version of Record online: 3 AUG 2007 | DOI: 10.1002/pola.22176

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      The first solvent-free synthesis of poly (N-methylolacrylamide) via free-radical frontal polymerization has been carried out. The experimental data are well-fitted by straight lines, which means that a constant-velocity, self-sustaining front was obtained. This is strong evidence that pure frontal polymerization is occurring. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    15. Hybrid free radical/cationic frontal photopolymerizations (pages 4331–4340)

      James V. Crivello

      Version of Record online: 7 AUG 2007 | DOI: 10.1002/pola.22177

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      The irradiation of hybrid photopolymer systems consisting of a free radically polymerizable multifunctional acrylate monomer and a cationically polymerizable epoxide or oxetane monomer was conducted under conditions where only the free radical polymerization takes place. This results in the formation of a free-standing polyacrylate network film containing quiescent oxonium ions along with the unreacted cyclic ether monomer. The subsequent application of a point source of heat to the film ignites a cationic ring-opening frontal polymerization that emanates from that site and propagates to all portions of the irradiated sample.

    16. Layer-by-layer assembly of weak-strong copolymer polyelectrolytes: A route to morphological control of thin films (pages 4341–4351)

      Elvira Tjipto, John F. Quinn and Frank Caruso

      Version of Record online: 3 AUG 2007 | DOI: 10.1002/pola.22179

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      Multilayer films comprising a copolymer of maleic acid and styrene sulfonate assembled in alternation with poly(diallyldimethylammonium chloride) were shown to rearrange significantly upon post-assembly variation of the pH. Depending on the assembly conditions used and the initial copolymer composition, thin polymer films containing either pores or interconnected ridges could be prepared. The film behavior was correlated to variations in the ionization of the carboxylate groups in the maleic acid moieties. The extent of rearrangement diminished with additional cycling of the pH. The approach presented is a simple method for controlling film morphology on the micro/nanoscale.

    17. Synthesis and properties of wholly aromatic polymers bearing cardo fluorene moieties (pages 4352–4363)

      Guey-Sheng Liou, Hung-Ju Yen, Yi-Ting Su and Hung-Yi Lin

      Version of Record online: 3 AUG 2007 | DOI: 10.1002/pola.22182

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      Three series of aromatic polyamides, polyesters and poly(1,3,4-oxadiazole)s containing bulky fluorene structures were prepared from 9,9-bis(4-carboxyphenyl)fluorene. All of the polymers were readily soluble in many organic solvents and showed useful thermal stability associated with high glass-transition temperatures in the range of 220–366 °C. These wholly aromatic polymer films were colorless, with high optical transparency, and exhibited UV-vis absorption bands at 266–348 nm and photoluminescence maximum bands at 368–457 nm within the purple to green region in N,N-dimethylacetamide (DMAc) solutions.

    18. Synthesis and characterization of 6- and 12-arm star polymers by nitroxide-mediated radical polymerization of St and MA from dendritic TIPNO-based hexafunctional and dodecafunctional macroinitiators (pages 4364–4376)

      Yozo Miura and Masamichi Dairoku

      Version of Record online: 6 AUG 2007 | DOI: 10.1002/pola.22183

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      Dendritic multifunctional macroinitiators having six and twelve TIPNO-based alkoxyamines, TIPNO-6 and TIPNO-12, were synthesized and the living radical polymerization of styrene, methyl acrylate, N,N-dimethylacrylamide, and isoprene from the macroinitiators were carried out. The polymerizations of St initiated with TIPNO-6 gave 6-arm star polymers with PDIs of 1.14–1.18, and the polymerizations of MA from TIPNO-6 and TIPNO-12 gave star polymers with PDIs of 1.08–1.18. The benzyl ether bonds of the poly(St) and poly(MA) star polymers were cleaved by treating them with Me3SiI or Pd/C, and the resulting arms' parts showed low PDIs of 1.19–1.25.

    19. Synthesis and optoelectronic properties of luminescent poly(p-phenylenevinylene) derivatives containing electron-transporting 1,3,4-oxadiazole groups (pages 4377–4388)

      Wen-Fen Su, Kun-Ming Yeh and Yun Chen

      Version of Record online: 3 AUG 2007 | DOI: 10.1002/pola.22184

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      A homopolymer (P0) and random copolymers (P1–P3) comprising phenylenevinylene and electron-transporting aromatic 1,3,4-oxadiazole (11, 18, 28 mol %, respectively) were prepared. The PL spectral results reveal that the aromatic 1,3,4-oxadiazole chromophores in P1–P3 suppress the intermolecular interactions. Their LUMO levels are reduced readily with increasing oxadiazole content (−2.7, −3.08, −3.11, and −3.19 eV, respectively). P1 shows the best EL performance (3490 cd/m2), and further increase in oxadiazole content results in microphase separation that leads to performance deterioration.

  2. Rapid Communications

    1. Top of page
    2. Articles
    3. Rapid Communications
    4. Notes
    1. You have free access to this content
      Synthesis of poly(vinyl ether) plastics for optical use by cationic copolymerization of tricyclodecyl vinyl ether with n-butyl vinyl ether (pages 4389–4393)

      Takeshi Namikoshi, Tamotsu Hashimoto and Michio Urushisaki

      Version of Record online: 7 AUG 2007 | DOI: 10.1002/pola.22205

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      Cationic copolymerizations of 8-vinyloxytricyclo[5.2.1.02,6]decane (TCDVE; tricyclodecane unit-containing vinyl ether) with n-butyl vinyl ether (NBVE) as a linear alkyl vinyl ether were undertaken in toluene solvent with living cationic initiators and BF3OEt2 as a non-living initiator. The Tg's of the copolymers of TCDVE and NBVE [poly(TCDVE-ran-NBVE)] was controlled by changing the copolymer composition. The copolymers showed similar transparency to those of polymethyl methacrylate (PMMA) and polycarbonate (PC), which are conventional optical plastics, and even lower specific gravity and water absorption than PMMA and PC. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

  3. Notes

    1. Top of page
    2. Articles
    3. Rapid Communications
    4. Notes
    1. You have free access to this content
      Polymerization of N-isopropylacrylamide in the presence of poly(acrylic acid) and poly(methacrylic acid) containing ω-unsaturated end-groups (pages 4394–4400)

      Ronan Mchale, Fawaz Aldabbagh, William M. Carroll and Bunichiro Yamada

      Version of Record online: 6 AUG 2007 | DOI: 10.1002/pola.22232

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      Poly(N-Isopropylacrylamide, NIPAM) propagating radicals add to acrylic acid (AA) macromonomer and methacrylic acid polymer containing unsaturated ω-end-group to respectively give novel graft copolymer (represented as • (AA) and ○ (NIPAM) units) and addition fragmentation chain transfer (AFCT). [Color figure can be viewed in the online issue, which is available at www.interscience.wiley. com.]

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