Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 45 Issue 7

1 April 2007

Volume 45, Issue 7

Pages 1185–1376

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      Perfluorocarbons: Life sciences and biomedical uses Dedicated to the memory of Professor Guy Ourisson, a true RENAISSANCE man. (pages 1185–1198)

      Marie Pierre Krafft and Jean G. Riess

      Version of Record online: 16 FEB 2007 | DOI: 10.1002/pola.21937

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      Phospholipids-coated perfluorocarbon-containing microbubbles and emulsion droplets (highly fluorinated shell components may also be present): the former are utilized as contrast agents for ultrasound diagnostic imaging, and the latter are investigated for oxygen delivery to tissues. Further biomedical uses of highly fluorinated materials include research tools for “abiotic” biology, targeted drug delivery, and reconstructive surgery. [A color version of the adjacent figure can be viewed in the online issue, which is available at]

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    1. Synthesis of new polyfluorene copolymers with a comonomer containing triphenylamine units and their applications in white-light-emitting diodes (pages 1199–1209)

      Sang Kyu Lee, Taek Ahn, Nam Sung Cho, Jeong-Ik Lee, Young Kwan Jung, Jonghee Lee and Hong Ku Shim

      Version of Record online: 15 FEB 2007 | DOI: 10.1002/pola.21892

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      A series of conjugated fluorene-based copolymers, poly[9,9-dihexylfluorene-2,7-diyl-co-(2,5-bis(4-diphenylaminostyryl)-phenylene-1,4-diyl)]s (PGs), bearing triphenylamine side chains were synthesized by nickel(0)-mediated polymerization. The triphenylamine group played an important role in reducing the energy barrier for the injection of holes from indium tin oxide. Moreover, an electroluminescence device fabricated with a blended polymer system of one of the PGs (PG10) and 1.0 wt % of a red-light-emitting polymer exhibited a nearly perfect white-light emission in a relatively broad bias range from 6 to 10 V.

    2. Anionic lanthanide phenoxide complexes as novel single-component initiators for the polymerization of ε-caprolactone and trimethylene carbonate (pages 1210–1218)

      Hongting Sheng, Liying Zhou, Yong Zhang, Yingming Yao and Qi Shen

      Version of Record online: 15 FEB 2007 | DOI: 10.1002/pola.21888

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      The anionic complexes [Ln(OAr)4][Na(DME)3]·DME (ArO = 2,6-di-tert-butyl-phenoxide; DME = dimethoxyethane) were found to be efficient single-component initiators for the ring-opening polymerization of ϵ-caprolactone and trimethylene carbonate, with much higher activity than that of the corresponding neutral complexes Ln(OAr)3(THF)2.

    3. Controlled radical polymerization of styrene mediated by the C-phenyl-N-tert-butylnitrone/AIBN pair: Kinetics and electron spin resonance analysis (pages 1219–1235)

      Valérie Sciannamea, Jean-Marie Catala, Robert Jérôme and Christophe Detrembleur

      Version of Record online: 15 FEB 2007 | DOI: 10.1002/pola.21889

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      This paper reports on the controlled radical polymerization of styrene at 110 °C, mediated by the PBN/AIBN pair according to a two-step process: a PBN/AIBN prereaction in toluene at 85 °C, the monomer polymerization at 110 °C. The prereaction has a key role on the polymerization control. Indeed, the amount of the in situ formed nitroxide and alkoxyamine strongly depends on the prereaction conditions, which directly affects the molecular weight of polystyrene. Combination of electron spin resonance (ESR), high pressure liquid chromatography (HPLC), and kinetics of polymerization allowed the nitroxide and alkoxyamine concentrations to be determined as well as the equilibrium constant K, the dissociation (kd), and the recombination (kc) rate constants and the activation energy Ea for the dissociation of the dormant form.

    4. Phenothiazine-S,S-dioxide- and fluorene-based light-emitting polymers: Introduction of e-deficient S,S-dioxide into e-rich phenothiazine (pages 1236–1246)

      Jonghee Lee, Jeong-Ik Lee, Moo-Jin Park, Young Kwan Jung, Nam Sung Cho, Hoon Je Cho, Do-Hoon Hwang, Sang-Kyu Lee, Jong-Hwa Park, Jiwon Hong, Hye Yong Chu and Hong-Ku Shim

      Version of Record online: 16 FEB 2007 | DOI: 10.1002/pola.21890

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      Poly(10-hexyl-phenothiazine-S,S-dioxide-3,7-diyl) and poly (9, 9′-dioctyl-fluorene-2,7-diyl-alt-10-hexyl-3,7-phenothiazine-S,S-dioxide) (PFPTZ-SS) copolymers were successfully synthesized through Yamamoto polymerization and Suzuki polymerization. The inclusion of SO2 moieties in the phenothiazine and fluorene copolymers changed the frontier orbital energy levels and presented an effective way of increasing the electron affinity of the copolymers. These phenothiazine-S,S-dioxide-based polymers showed higher glass transition temperatures than pristine polyfluorene and exhibited strong florescence with bright blue emissions in the solid state. Additionally, we provide an explanation for the higher electroluminescence properties of PFPTZ-SS in light-emitting diode devices. These findings thus establish a strategy for improving the light-emitting properties of polyfluorene derivatives, which may eventually prove useful in polymeric light-emitting diode device applications.

    5. Supramolecular inclusion complexation of polyhedral oligomeric silsesquioxane capped poly(ε-caprolactone) with α-cyclodextrin (pages 1247–1259)

      Yong Ni and Sixun Zheng

      Version of Record online: 15 FEB 2007 | DOI: 10.1002/pola.21893

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      A tadpole-like poly(ϵ-caprolactone) was synthesized via the ring-opening polymerization of ϵ-caprolactone with 3-hydroxypropylheptaphenyl polyhedral oligomeric silsesquioxane as an initiator. The organic–inorganic polyhedral oligomeric silsesquioxane capped poly(ϵ-caprolactone) was used to prepare supramolecular inclusion complexes with α-cyclodextrin. Only when the poly(ϵ-caprolactone) chains were shorter did the efficiency of the inclusion complexation decrease, and this could be attributed to the lower mobility of the bulky polyhedral oligomeric silsesquioxane group, which restricted the motion of the poly(ϵ-caprolactone) chain attached to the silsesquioxane cage.

    6. Potassium enolates of N,N-dialkylamides as initiators of anionic polymerization (pages 1260–1271)

      Takashi Ishizone, Daizaburo Yashiki, Motoyasu Kobayashi, Takashi Suzuki, Mana Ito and Seiichi Nakahama

      Version of Record online: 15 FEB 2007 | DOI: 10.1002/pola.21896

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      The relative nucleophilicity, basicity, and ease of preparation of a series of α-potassio-N,N-diethylamides [α-potassio-N,N-diethylacetamide (1), α-potassio-N,N-diethylpropionamide (2), and α-potassio-N,N-diethylisobutyramide (3)] as novel anionic initiators were demonstrated. These amide enolates could initiate the anionic polymerizations of styrene and 2-vinylpyridine, although the efficiencies were not quantitative. On the other hand, 13 quantitatively initiated the controlled polymerizations of polar monomers such as methyl methacrylate and N,N-diethylacrylamide in the presence of diethylzinc. The resulting polymers possessed narrow molecular weight distributions and predicted molecular weights. These new enolate initiators allowed us to synthesize well-defined poly(N,N-diethylacrylamide)s without a hydrophobic terminal moiety because the initiator residue was completely the same as the repeating unit.

    7. 2-Cyanoprop-2-yl dithiobenzoate mediated reversible addition–fragmentation chain transfer polymerization of acrylonitrile targeting a polymer with a higher molecular weight (pages 1272–1281)

      Xiao-Hui Liu, Yan-Guo Li, Ying Lin and Yue-Sheng Li

      Version of Record online: 15 FEB 2007 | DOI: 10.1002/pola.21899

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      The reversible addition–fragmentation chain transfer polymerization of acrylonitrile with 2-cyanoprop-2-yl dithiobenzoate as a chain-transfer agent was investigated in detail for the purpose of synthesizing polyacrylonitrile with a high molecular weight and a low polydispersity index. The various experimental parameters, including the solvent, the temperature, the molar ratio of dithiobenzoate to the initiator, the molar ratio of the monomer to dithiobenzoate, the monomer concentration, and the addition of the comonomer, were varied to improve the control of the polymerization. Polyacrylonitrile with a high molecular weight up to 32,800 and a polydispersity index as low as 1.29 was obtained for the first time.

    8. Novel route to styrene/p-aminostyrene copolymers (pages 1282–1286)

      Christopher A. Lukey, Michaela Tymichova and Hugh R. Brown

      Version of Record online: 15 FEB 2007 | DOI: 10.1002/pola.21894

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      A procedure is described for the synthesis of random copolymers of styrene and p-aminostyrene, whereby amino functionality is introduced into polystyrene via a simple two-step process. This process involves bromination followed by palladium-catalyzed conversion to the corresponding amine. The resultant copolymer has a precisely known molecular weight and polydispersity.

    9. Factors affecting the sensitivity to acid inhibition in novel acrylates characterized by secondary functionalities (pages 1287–1295)

      Harini Kilambi, Daniel Konopka, Jeffrey W Stansbury and Christopher N Bowman

      Version of Record online: 15 FEB 2007 | DOI: 10.1002/pola.21897

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      This study indicates for the first time that a broad range of acrylates exhibit significant rate reductions in the presence of protic acid concentrations 0.1–0.5 wt %. Furthermore, dramatically different sensitivities to acid inhibition, differing by up to 1–2 orders of magnitude, have been observed for various acrylates, depending on the monomer structure. Acid inhibition studies conducted in the presence of propylene carbonate have indicated only a twofold increase in the parameters associated with acid inhibition in comparison with an increase of 2 orders of magnitude for novel acrylates characterized by carbamate and carbonate functionalities.

    10. Thymine-based, water-soluble phototerpolymers: Their preparation and synthesis (pages 1296–1303)

      Jason R. Bianchini, Kei Saito, Taylor B. Balin, Vineet Dua and John C. Warner

      Version of Record online: 15 FEB 2007 | DOI: 10.1002/pola.21901

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      The synthesis, thermal degradation, and structure–activity relationship of a series of novel photoreactive terpolymers containing vinylbenzylthymine, vinylbenzyltriethylammonium chloride, and N-butyl-N,N-dimethyl-(4-vinylbenzyl)ammonium chloride are described. Terpolymers with different monomer ratios have been prepared and immobilized on glass slides via the UV-photoinitiated crosslinking of the thymine moieties. An analysis of the relationship between the monomer ratio and the surface properties of the resulting photoresists has demonstrated that we can easily control the hydrophobicity by varying the monomer ratios. Thermogravimetric analysis has revealed that the terpolymers have two degradation stages corresponding to the quaternary ammonium pendant groups and to the thymine.

    11. Asymmetric radical polymerization and copolymerization of N-(1-phenyldibenzosuberyl)methacrylamide and its derivative leading to optically active helical polymers (pages 1304–1315)

      A. K. M. Fakhrul Azam, Masami Kamigaito and Yoshio Okamoto

      Version of Record online: 15 FEB 2007 | DOI: 10.1002/pola.21902

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      N-(1-Phenyldibenzosuberyl)methacrylamide(PDBSMAM) and its derivative N-[(4-butylphenyl)dibenzosuberyl]methacrylamide (BuPDBSMAM) were synthesized and polymerized in the presence of (+)- and (−)-menthols at different temperatures. The tacticity of the polymers was estimated to be nearly 100%isotactic from the 1H NMR spectra of polymethacrylamides derivedin D2SO4. The copolymerization of BuPDBSMAM witha small amount of optically active N-[(R)-(+)-1-(1-naphthyl)ethyl]methacrylamide [(+)-NEMAM], particularly in the presence of (−)-menthol,produced a polymer with a high optical activity. The one-handedhelicity may be efficiently induced in the copolymer.

    12. Synthesis of water-dispersible, fluorinated particles with grafting sulfonate chains by the core crosslinking of block copolymer micelles (pages 1316–1323)

      Kozo Matsumoto, Shuji Kage and Hideki Matsuoka

      Version of Record online: 21 FEB 2007 | DOI: 10.1002/pola.21903

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      Fluorinated polymer particles with grafting sulfonate chains, which showed high dispersion stability in aqueous media, were synthesized by the core crosslinking of block copolymer micelles. A crosslinkable block copolymer, poly[(2,3,4,5,6-pentafluorostyrene)-co-4-(1-methylsilacyclobutyl)styrene]-b-poly(neopentyl 4-styrenesulfonate), composed of a statistical copolymer segment of pentafluorostyrene with 4-(1-methylsilacyclobutyl)styrene and a neopentyl 4-styrenesulfonate segment, was prepared by the nitroxy-mediated living radical polymerization of a pentafluorostyrene/4-(1-methylsilacyclobutyl)styrene mixture and neopentyl 4-styrenesulfonate.

    13. UV curing of a novel resin derived from poly(ethylene terephthalate) (pages 1324–1335)

      Auvergne R., Saint-Loup R., Joly-Duhamel C., Robin J. J. and Boutevin B.

      Version of Record online: 15 FEB 2007 | DOI: 10.1002/pola.21904

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      New photopolymerizable unsaturated polyester resins based on PET waste are described. These resins came from glycolysis of PET and were functionalized by a methyl hemiester of maleic acid. In the presence of an electron donnor monomer as divinyl ether, these oligomers were copolymerized under UV irradiation. The reaction was monitored in situ by realtime IR spectroscopy to study the kinetics of photopolymerization.

    14. Xanthene dye functionalized norbornenes for the use in ring opening metathesis polymerization (pages 1336–1348)

      Martina Sandholzer, Alexandra Lex, Gregor Trimmel, Robert Saf, Franz Stelzer and Christian Slugovc

      Version of Record online: 15 FEB 2007 | DOI: 10.1002/pola.21905

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      A convenient synthetic route towards polymerizable xanthene dyes and the preparation of dye-functionalized ROM-copolymers are presented. The acid/base sensitive behavior of the dyes was preserved in the monomers and in copolymers as revealed by UV–Vis and luminescence measurements.

    15. Immobilization of aminothiols on poly(oxyethylene H-phosphonate)s and poly(oxyethylene phosphate)s—An approach to polymeric protective agents for radiotherapy of cancer (pages 1349–1363)

      Kolio Troev, Ivelina Tsatcheva, Neli Koseva, Radostina Georgieva and Ivan Gitsov

      Version of Record online: 15 FEB 2007 | DOI: 10.1002/pola.21906

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      Polymer complexes of poly(oxyethylene H-phosphonates) or poly(oxyethylene phosphates) and the clinically approved aminothiol-based radioprotectors amifostine WR-1065 are formed by Atherton-Todd reaction, ion bond- or hydrogen bond formation. The structure of the complexes is elucidated by NMR and FTIR analyses.

    16. Propylene polymerizations with a binary metallocene system—Chain shuttling caused by trimethylaluminium between active catalyst centers (pages 1364–1376)

      Antti Tynys, Jan L. Eilertsen, Jukka V. Seppälä and Erling Rytter

      Version of Record online: 15 FEB 2007 | DOI: 10.1002/pola.21908

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      Chain shuttling between catalyst sites was confirmed when a binary metallocene system was used in propylene polymerization at varying TMA concentration. It was demonstrated that the chain shuttling caused changes in (i) catalyst activity, (ii) low and high Mw peak maximums, (iii) melting behavior, and (iv) polymer microstructure. It was affirmed that TMA worked as a chain shuttling agent, and a stereoblock copolymer was formed.