Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 43 Issue 24

15 December 2005

Volume 43, Issue 24

Pages 6179–6618

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      Experimental techniques in high-vacuum anionic polymerization (pages 6179–6222)

      David Uhrig and Jimmy W. Mays

      Version of Record online: 21 OCT 2005 | DOI: 10.1002/pola.21016

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      A thorough compilation of high-vacuum techniques is provided, including many sketches of all-glass apparatuses accompanied by step-by-step procedural accounts.

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    1. Preparation of new π-conjugated polypyrroles by organometallic polycondensations. Synthesis of N-BOC (t-butoxycarbonyl) and N-phenylethynyl polymers, thermal deprotection of the BOC Group, and packing structure of the N-phenylethynyl polymer (pages 6223–6232)

      Takakazu Yamamoto, Masataka Yoshizawa, Abla Mahmut, Masahiro Abe, Shin-ichi Kuroda, Tatsuya Imase and Shintaro Sasaki

      Version of Record online: 21 OCT 2005 | DOI: 10.1002/pola.21080

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      New polypyrroles were prepared by organometallic polycondensations. Deprotection of the BOC group of PPr(3-Hep; N-BOC) proceeded at 150 °C to give poly(3-heptylpyrrole). XRD (X-ray diffraction) data of Copoly-2 indicated that Copoly-2 assumed a stacked structure in the solid.

    2. Multicyclic polyethers with pendant keto groups by polycondensation of silylated 1,1,1-tris(4-hydroxyphenyl)ethane (pages 6233–6246)

      Hans R. Kricheldorf, Lali Vakhtangishvili, Gert Schwarz and Marc Prosenc

      Version of Record online: 21 OCT 2005 | DOI: 10.1002/pola.21096

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      Silylated 1,1,1-tris(4-hydroxyphenyl)ethane was polycondensed with 2,4- and 2,6-difluoroacetophenone or with 2,4- and 2,6-difluorobenzophenone. Polycondensation of the 2,4-isomers involved a high cyclization tendency so that gelation was avoided and almost quantitative yields of multicyclic polyethers were obtained.

    3. Solvent effect on the atom transfer radical polymerization of allyl methacrylate (pages 6247–6261)

      Rodrigo París and José Luis de la Fuente

      Version of Record online: 21 OCT 2005 | DOI: 10.1002/pola.21111

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      The atom transfer radical polymerization of allyl methacrylate at 70 °C in solution showed a general kinetic behavior, which presented a well-controlled early stage until a deceleration process took place, achieving a limit conversion. Both the gel formation and the limit conversion were strongly dependent on different experimental parameters, such as the polar character of the solvent employed, the initial monomer dilution degree, and the type of halide used as a catalyst. Moreover, the livingness of these homopolymerizations was probed through chain-extension experiments with the bromo-terminated poly(allyl methacrylate)s obtained.

    4. Synthesis of cyclic methacrylic acid oligomers by atom transfer radical polymerization (pages 6262–6271)

      Reiko Saito and Kazutaka Yamaguchi

      Version of Record online: 21 OCT 2005 | DOI: 10.1002/pola.21084

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      Poly(methacrylic acid) (PMAA) oligomers were synthesized by combining template polymerization and copper-mediated atom transfer radical polymerization with multivinyl monomer of β-cyclodextrin (CD) having 20.4 methacryloyl groups on both primary and secondary hydroxyl group sides of CD scaffold, with 1,3-dibromobutane as an initiator. The initiation and propagation sites of polymerized sequence of CD were connected by postpolymerization of polymerized products with CuBr and tris[(2-dimethylamino)ethyl]amine (Me6TREN) in a methanol/water mixture of 10 wt% of water. PMAA oligomers were detached from β-CD scaffold by hydrolysis. Three types of cyclic PMAA were obtained by postpolymerization.

    5. Polyimides based on new diamines having pendant imide groups (pages 6272–6281)

      Hans R. Kricheldorf, Shu-chin Fan, Lali Vakhtangishvili, Gert Schwarz and Detlef Fritsch

      Version of Record online: 21 OCT 2005 | DOI: 10.1002/pola.21087

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      Starting out from 4,5-dichlorophthalic anhydride, a new class of aromatic diamines with pendant imide groups was synthesized. Polycondensation of these diamines with dianhydrides in m-cresol yielded cyclic polyimides having various pendant aliphatic and aromatic groups including tertiary amines.

    6. Salt effect on polyaddition of bifunctional cyclic carbonate and diamine (pages 6282–6286)

      Bungo Ochiai, Shoko Inoue and Takeshi Endo

      Version of Record online: 21 OCT 2005 | DOI: 10.1002/pola.21081

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      Various salts effectively accelerated polyaddition of bifunctional cyclic carbonate and diamine giving poly(hydroxyurethane). The acceleration achieved the synthesis of poly-(hydroxyurethane)s with the higher molecular weight without coloration.

    7. Highly selective oxidative cross-coupling polymerization with copper(I)-bisoxazoline catalysts (pages 6287–6294)

      Tomohisa Temma and Shigeki Habaue

      Version of Record online: 21 OCT 2005 | DOI: 10.1002/pola.21086

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      The asymmetric oxidative coupling polymerization of methyl 6,6′-dihydroxy-2,2′-binaphthalene-7-carboxylate with the copper-diamine catalysts under an O2 atmosphere was carried out. As is the case with the CuCl-2,2′-(S)-isopropylidenbis(4-phenyl-2-oxazoline) [(S)IPhO] catalyst, a polymer with a high cross-coupling selectivity of 96% was obtained in 71% yield, whose THF-soluble part had a number-average molecular weight of 4.5 × 103. To estimate the enantioselectivity with respect to the cross-coupling linkage in the obtained polymer, the model asymmetric oxidative cross-coupling reaction with CuCl-(S)IPhO was also conducted, and the products showed a 94% cross-coupling selectivity and an enantioselectivity of 31% ee (S).

    8. Novel organic–inorganic hybrid materials from renewable resources: Hydrosilylation of fatty acid derivatives (pages 6295–6307)

      G. Lligadas, L. Callau, J. C. Ronda, M. Galià and V. Cádiz

      Version of Record online: 21 OCT 2005 | DOI: 10.1002/pola.21039

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      Novel hybrid organic–inorganic materials were prepared from 10-undecenoyl triglyceride and methyl 3,4,5-tris(10-undecenoyloxy)benzoate via hydrosilylation. As crosslinkers, 1,4-bis(dimethylsilyl)benzene, tetrakis(dimethylsilyloxy)silane, and 2,4,6,8-tetramethylcyclotetrasiloxane were used. The hydrosilylation reaction was catalyzed by Karstedt's catalyst [Pt(0)–divinyltetramethyldisiloxane complex]. For the structural characterization of the networks, Fourier transform infrared, 13C NMR, and 29Si magic-angle-spinning NMR were used. The thermal properties of these hybrids were studied with differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical analysis. The obtained materials showed good transparency and promising properties for optical applications.

    9. Polymers from a levopimaric acid–acrylonitrile Diels–Alder adduct: Synthesis and characterization (pages 6308–6322)

      Ioan Bicu and Fanica Mustata

      Version of Record online: 21 OCT 2005 | DOI: 10.1002/pola.21070

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      New polyamides and polyesters, having molecular weights up to 10,000, were obtained by the polycondensation of the Diels–Alder adduct between levopimaric acid and acrylonitrile (AN), or its ketone derivative, with suitable diamines or diols. This article describes the route from the natural resin acids to polymers via Diels–Alder adducts. The philodiene was AN. The insertion of the pseudoaromatic hydrophenanthrene moieties into the polymer chains led to enhanced thermal and hydrophobic properties.

    10. Ethylene/α-olefin copolymerization with bis(β-enaminoketonato) titanium complexes activated with modified methylaluminoxane (pages 6323–6330)

      Li-Ming Tang, Tao Hu, Li Pan and Yue-Sheng Li

      Version of Record online: 26 OCT 2005 | DOI: 10.1002/pola.21112

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      A series of new titanium complexes {[(Ph)NC(R2)CHC-(R1)O]2TiCl2} have been investigated as precatalysts for the copolymerization of ethylene with α-olefins (i.e., 1-hexene, 1-octene, allylbenzene, and 4-phenyl-1-butene) in the presence of modified methylaluminoxane.

    11. The LEGO toolbox: Supramolecular building blocks by nitroxide-mediated controlled radical polymerization (pages 6331–6344)

      Bas G. G. Lohmeijer and Ulrich S. Schubert

      Version of Record online: 28 OCT 2005 | DOI: 10.1002/pola.20967

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      A terpyridine-functionalized alkoxyamine unimolecular initiator was used for the nitroxide-mediated polymerization of n-butylacrylate, N,N-dimethylacrylamide, 4-vinylpyridine, 2-vinylpyridine, and isoprene, rendering polymers that are valuable building blocks for macromolecular metallo-supramolecular architectures.

    12. Synthesis of water-soluble cationic polymers with star-like structure based on cyclodextrin core via ATRP (pages 6345–6354)

      Jianshu Li, Huining Xiao, Young Shin Kim and Tao Lu Lowe

      Version of Record online: 28 OCT 2005 | DOI: 10.1002/pola.21058

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      A series of novel cationic star-like polymers (Star-P(MeDMA)s) with 21 arms were synthesized through atom transfer radical polymerization (ATRP) by core-first method, using a β-cyclodextrin initiator. The molecular weights, hydrodynamic sizes, and charge densities of the quaternized polymers were characterized. The results demonstrated that the moderate aqueous solubility of the β-cyclodextrin initiator had significant effects on the physicochemical properties of the obtained star polymers. The polymerization of 500/1/2/5 ([M]0/[I]0/[Cu(I)0/[L]0]) at 90 °C for 6h was found to be the best condition to synthesize the proposed cationic star polymer with well-defined structures in aqueous medium.

    13. Peptide–polymer vesicles prepared by atom transfer radical polymerization (pages 6355–6366)

      Lee Ayres, P. Hans, J. Adams, Dennis W. P. M. Löwik and Jan C. M. van Hest

      Version of Record online: 31 OCT 2005 | DOI: 10.1002/pola.21107

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      A bifunctional peptide-based initiator for atom transfer radical polymerization was prepared with solid-phase peptide synthesis. This peptide-based initiator was then used to initiate the controlled polymerization of methyl methacrylate. The resulting triblock copolymer, upon suspension in tetrahydrofuran and the subsequent addition of water, formed a mixture of polymersomes and large compound micelles. These aggregates were investigated with electron microscopy, and the secondary conformation of the peptide was investigated with infrared spectroscopy. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    14. Synthesis of poly(styrene-block-tert-butyl acrylate) star polymers by atom transfer radical polymerization and micellization of their hydrolyzed polymers (pages 6367–6378)

      Sinoj Abraham, Chang-Sik Ha and Il Kim

      Version of Record online: 28 OCT 2005 | DOI: 10.1002/pola.21082

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      A series of poly(styrene-block-tert-butyl acrylate) heteroatom star block copolymers having various block lengths were prepared by atom transfer radical polymerization (ATRP), using an “as synthesized” cynurate modified trifunctional initiator. The block copolymers were chemically modified so as to accomplish hydrophilic nature. The associating behavior of these copolymers was investigated by light scattering, viscometry, and field emission SEM. The determination of cmtvalues at different concentrations enabled to study the enthalpy of micellization and it seems to be negative, favoring the micellization phenomenon. The combination of the experimental techniques used herein made investigations of the association parameters, the thermodynamic properties, and the micellar structure of the amphiphilic PS-b-PAA star block copolymers feasible.

    15. Dendrimer-star polymer and block copolymer prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization with dendritic chain transfer agent (pages 6379–6393)

      Chun-Yan Hong, Ye-Zi You, Jun Liu and Cai-Yuan Pan

      Version of Record online: 28 OCT 2005 | DOI: 10.1002/pola.21098

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      A dendritic polyester with 16 dithiobenzoate terminal groups was synthesized and used as multifunctional RAFT agent in the RAFT polymerization of styrene (St); 16-armed dendrimer-star PSts have been successfully prepared. The polymerization is of living characters, and thus, the chain length of each PSt arms in the dendrimer-star macromolecules and the molecular weight of the polymers obtained can be controlled; the polydispersities are narrow. The dendrimer-star PSt was used as macro RAFT agent in the successive RAFT polymerization of methyl acrylate (MA); dendrimer-star block copolymers of St and MA with well-defined molecular weights and narrow polydispersities were successfully prepared.

    16. Aromatic homo- and copolyesters from naturally occurring monosaccharides: PET and PEI analogs derived from L-arabinitol and xylitol (pages 6394–6410)

      Francisca Zamora, Khalid Hakkou, Abdelilah Alla, José L. Espartero, Sebastián Muñoz-Guerra and Juan A. Galbis

      Version of Record online: 28 OCT 2005 | DOI: 10.1002/pola.21045

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      The synthesis and characterization of new aromatic homo- and copolyesters based on L-arabinitol and xylitol are described. These polymers were obtained by polycondensation reaction of the 2,3,4-tri-O-methyl-l-arabinitol (1A) or 2,3,4- tri-O-methyl-xylitol (1X), or their mixtures with ethylene glycol, with terephthaloyl chloride or isophthaloyl chloride in o-dichlorobenzene or in the melt phase from the corresponding methyl phthalates. By contrast with PET and PEI, these new homo- and copolyesters containing 20% or more of pentitol units were soluble in tetrahydrofuran, chloroform, and polar aprotic solvents such as DMF or DMSO and showed a significant hygroscopicity. DSC and TGA studies showed that the melting temperature of polyethylene terephthalate is depressed by the presence of pentitol units, whereas the thermal stability is kept above 350 °C.

    17. Synthesis and properties of sulfonated poly(arylene ether) containing tetraphenylmethane moieties for proton-exchange membrane (pages 6411–6418)

      L. Wang, Y. Z. Meng, S. J. Wang, X. H. Li and M. Xiao

      Version of Record online: 31 OCT 2005 | DOI: 10.1002/pola.21053

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      Novel sulfonated poly(arylene ether)s containing tetraphenylmethane moieties were successfully synthesized by the sulfonation of the polymer using chlorosulfonic acid as sulfonation agent. The sulfonation took place only at the para position on the pendant phenyl rings. The sulfonation degree can be easily controlled by using different ratios of sulfonation agent to polymer repeating unit. The polymeric ionomers form tough membranes with excellent thermal and oxidative stability. The film from polymer 2c with high sulfonation degree showed greater water affinity and higher proton conductivity than Nafion 117, which makes it an excellent candidate for polymer electrolyte membrane fuel cells.

    18. Synthesis, polymerization, and effects on the flame retardancy of boron-containing styrenic monomers (pages 6419–6430)

      C. Martín, B. J. Hunt, J. R. Ebdon, J. C. Ronda and V. Cádiz

      Version of Record online: 31 OCT 2005 | DOI: 10.1002/pola.21122

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      A boron-containing styrenic monomer, 5-benzyl-2-phenyl-5-(4-vinylbenzyl)-[1,3,2]-dioxaborinane (2), was synthesized to study the influence of boron on the properties of the homopolymer and copolymer with styrene. A similar monomer without boron (1) was also prepared and polymerized so that their properties could be compared with the aforementioned boron-containing polymers. These monomers were characterized by elemental analysis, mass spectrometry, Fourier transform infrared, and 1H and 13C NMR. The boron-containing polymers had higher limiting oxygen indices and gave greater yields of char than those without boron.

    19. Noncovalent synthesis of supramolecular dendritic architectures in water (pages 6431–6437)

      Maarten A. C. Broeren, Jeffrey G. Linhardt, Hinke Malda, Bas F. M. de Waal, Ron M. Versteegen, Joris T. Meijer, Dennis W. P. M. Löwik, Jan C. M. van Hest, Marcel H. P. van Genderen and E. W. Meijer

      Version of Record online: 31 OCT 2005 | DOI: 10.1002/pola.21068

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      A supramolecular synthesis is described to obtain stable dendritic aggregates in water. A poly(ethylene glycol) containing guest molecule is able to bind to urea–adamantyl-modified poly(propylene imine) dendrimers in chloroform in a noncovalent manner, and can solubilize the hydrophobic dendrimer in water when chloroform is removed and D2O is added. This methodology opens the way to functional dendrimer aggregates in aqueous media.

    20. Synthesis and polymerization of (E)-p-[(p-methoxyphenyl)-2-ethenyl]phenylacetylene with Ziegler–Natta, rhodium, and palladium complexes (pages 6438–6444)

      J. Gonzalo Rodríguez, Antonio Lafuente and Javier Arranz

      Version of Record online: 27 OCT 2005 | DOI: 10.1002/pola.21120

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      The synthesis and polymerization of (E)-p-[(p-methoxyphenyl)-2-ethenyl]phenylacetylene was carried out with a homogeneous vanadium acetylacetonate/aluminum triethyl catalyst system, a bis(rhodium chloride cycloocta-1,5-diene) complex, and a palladium/trimethylsilyl complex. In all cases, the main fraction was a polymer with a stereoregular structure. The polymerization with the vanadium catalyst gave a polymer fraction in a low yield. The polymerization of (E)-p-[(p-methoxyphenyl)-2-ethenyl]phenylacetylene with the soluble rhodium complex gave a polymer in a high yield. The soluble palladium/chlorotrimethylsilane complex gave a polymer in a good yield. On the basis of the spectroscopic data, the poly{(E)-p-[(p-methoxyphenyl)-2-ethenyl]phenylacetylene)} obtained, in all cases, showed a cis–transoidal stereoregular structure. The molecular mass of poly{(E)-p-[(p-methoxyphenyl)-2-ethenyl]phenylacetylene)} was determined by the matrix-assisted laser desorption/ionization time-of-flight technique. The kinetics of the reaction were analyzed.

    21. Synthesis and properties of poly(heteroaryleneethynylene)s consisting of electron-accepting benzothiadiazole/quinoxaline units and electron-donating alkyl thiophene units (pages 6445–6454)

      Raja Shahid Ashraf and Elisabeth Klemm

      Version of Record online: 31 OCT 2005 | DOI: 10.1002/pola.21089

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      Low-band-gap, π-conjugated polymers composed of π-excessive thiophene and π-deficient benzothiadiazole and quinoxaline units were prepared in high yields by a polycondensation method using the Sonogashira cross-coupling reaction. The copolymers were characterized by NMR, IR, UV, gel permeation chromatography, and elemental analysis. The absorption and emission in solution and in the solid state of the polymers revealed that the polymers generated a π-stacked structure in the solid state, and the polymer molecules in the film were ordered. Thin films of poly[3-dodecylthiophen-2,5-diylethynylene-(benzo[1,2,5]thiadiazole-4,7-diyl)ethynylene] (P-1), poly[3,4-didodecylthiophen-2,5-diylethynylene-(benzo[1,2,5]thiadiazole-4,7-diyl)ethynylene] (P-2), poly[3-dodecylthiophene-2,5-diylethynylene-(2,3-dipyridine-2-ylquinoxaline-5,8-diyl)ethynylene] (P-3), and poly[3,4-didodecylthiophene-2,5-diylethynylene-(2,3-dipyridine-2-ylquinoxaline-5,8-diyl)ethynylene] (P-4) exhibited an optical band gap of ∼1.85–2.08 eV. The absorption spectra of P-2 and P-4 at different temperatures also revealed significant effects of the structure on the molecular interactions.

    22. Reactions of Me2Si(2-Me-4,5-BenzInd)Zr(Cl)(NEt2) and Me2Si(2-Me-4,5-BenzInd)ZrCl2 (BenzInd = benzindenyl) with trimethylaluminum and methylaluminumoxane: Correlation of spectroscopy and propene polymerizations (pages 6455–6464)

      Tanja Seraidaris, Barbro Löfgren, Tuulamari Helaja, Tiina Vanne and Nora Mäkelä-Vaarne

      Version of Record online: 31 OCT 2005 | DOI: 10.1002/pola.21125

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      The activity of metallocene/methylaluminumoxane (MAO) catalysts in olefin polymerization is highly dependent on both the alkylation and activation of the complexes. The leaving ligands have an important role in the complex activation, influencing the activity of the system. In this work, the reactions of complexes Me2Si(2-Me-4,5-BenzInd)2ZrCl2 (BenzInd = benzindenyl) and Me2Si(2-Me-4,5-BenzInd)2-Zr(Cl)(NEt2) with trimethylaluminum (TMA) and MAO were studied with ultraviolet–visible and NMR spectroscopy. In addition, the polymerization behavior of the different species was investigated in propene polymerizations.

    23. Synthesis of phenylquinoxaline oligomers containing pendant electron-donating and electron-withdrawing groups (pages 6465–6479)

      Jong-Beom Baek and Frank W. Harris

      Version of Record online: 31 OCT 2005 | DOI: 10.1002/pola.21119

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      A novel series of extended 6-substituted quinoxaline AB monomer mixtures were synthesized and polymerized to afford phenylquinoxaline oligomers containing electron-donating and electron-withdrawing groups. The properties of the monomers and resultant oligomers dramatically depended on the polarity of the pendant groups. The monomers and oligomers displayed high fluorescence in tetrahydrofuran and N-methyl-2-pyrrolidinone solutions, respectively.

    24. Synthesis and characterization of new polyamides based on Diphenylaminoisosorbide (pages 2480–2491)

      Asmaa A. Caouthar, Andre Loupy, Michel Bortolussi, Jean-claude Blais, Ludovic Dubreucq and Abdelkrim Meddour

      Version of Record online: 27 OCT 2005 | DOI: 10.1002/pola.21116

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      New optically active aromatic polyamides were synthesized by the microwave-assisted polycondensation of an optically active isosorbide-derived diamine with different diacyl chlorides in the presence of a small amount of a polar organic solvent such as N-methylpyrrolidinone. The use of such conditions was necessary to induce effective homogeneous heating of the monomers and subsequent polycondensation leading to the formation of polymers with inherent viscosities between 0.22 and 0.73 dL/g, that is, with rather high molecular weights up to 140,000 g/mol. With interfacial polymerization or the Higashi method, lower molecular weight polymers were obtained with inherent viscosities in the range of 0.04–0.36 dL/g (the maximum molecular weight was ca. 29,000 g/mol). Differential scanning calorimetry measurements clearly demonstrated the high thermal stability of these polymers by the range of the melting points (180–300 °C) and the absence of decomposition.

    25. Synthesis and crosslinking reaction of poly(thiourethane)s having a siloxane moiety in the side chain (pages 6492–6502)

      Kazuya Uenishi, Atsushi Sudo and Takeshi Endo

      Version of Record online: 1 NOV 2005 | DOI: 10.1002/pola.21123

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      A polyaddition reaction consisting of three components—(1) a 5-membered cyclic dithiocarbonate having a siloxane moiety (DTC–Si), (2) a diamine, and (3) a diisocyanate—was carried out. The side chain of the resulting poly(thiourethane)s inherited the siloxane group from DTC–Si, the condensation reaction of which made them efficiently crosslinked and permanently immobilized on a silicate surface.

    26. Polymerization of n-hexyl isocyanate with CpTiCl2(OR) (R = functional group or macromolecular chain): A route to ω-functionalized and block copolymers and terpolymers of n-hexyl isocyanate (pages 6503–6514)

      Stylianos Mourmouris, Konstantinos Kostakis, Marinos Pitsikalis and Nikos Hadjichristidis

      Version of Record online: 1 NOV 2005 | DOI: 10.1002/pola.21129

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      A combination of anionic and organotitanium-initiated polymerization afforded well-defined diblock copolymers of n- hexyl isocyanate with styrene, PS-b-PHIC [PS = polystyrene; PHIC = poly(n-hexyl isocyanate)], and triblock terpolymers with styrene and isoprene, PS-b-PI-b-PHIC and PI-b-PS-b-PHIC (PI = polyisoprene), as well as ω-cholesteryl poly(n-hexyl isocyanate).

    27. New family of highly emissive, soluble poly(1,4-fluorenylenevinylene) derivatives: Synthesis and characterization (pages 6515–6523)

      Yun-Hi Kim, Dong-Cheol Shin, Hyung-Sun Kim, Hong You and Soon-Ki Kwon

      Version of Record online: 1 NOV 2005 | DOI: 10.1002/pola.21126

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      A new poly(arylene vinylene) derivative, poly(1,4-fluorenylenevinylene), with the advantages of poly(p-phenylene vinylene) and polyfluorene (PF), was designed, synthesized, and characterized. The polymer formed a defect-free structure with a number-average molecular weight of 32,600. The polymer was amorphous with high thermal stability and with a high glass-transition temperature (200 °C). The polymer film showed a maximum emission at 515 nm with a photoluminescence efficiency of 58 ± 5%.

    28. Free-radical polymerization of styrene with p-nitrobenzyl triphenyl phosphonium ylide as an initiator (pages 6524–6533)

      Kiran Prajapati and Anuradha Varshney

      Version of Record online: 1 NOV 2005 | DOI: 10.1002/pola.20708

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      The free-radical polymerization of styrene with p-nitrobenzyl triphenyl phosphonium ylide (p-NBTPY) as an initiator in dioxane at 80 ± 1 °C in a dilatometer under a nitrogen atmosphere for 150 min resulted in a syndiotactic polymer, as evidenced by an IR band at 1027 cm−1 and a δ value of 145.3 in a 13C NMR spectrum. A 1H NMR spectrum showed the methylene protons as triplets. The system followed ideal kinetics. The overall activation energy and kp2/kt (kp = propagation rate constant; kt = termination rate constant) values were 47 kJ/mol and 1.33 × 10−2 L/mol−1 s−1, respectively. Electron spin resonance spectroscopy confirmed initiation by a phenyl radical. Differential scanning calorimetry studies showed the glass-transition temperature of the polymer to be 342 K.

    29. Amphiphilic star-block copolymers based on a hyperbranched core: Synthesis and supramolecular self-assembly (pages 6534–6544)

      Zhifeng Jia, Yongfeng Zhou and Deyue Yan

      Version of Record online: 1 NOV 2005 | DOI: 10.1002/pola.21128

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      Novel amphiphilic star-block copolymers, star poly(caprolactone)-block-poly[(2-dimethylamino)ethyl methacrylate] and poly(caprolactone)-block-poly(methacrylic acid), with hyperbranched poly(2-hydroxyethyl methacrylate) as a core moiety were successfully synthesized by a combination of ring-opening polymerization and atom transfer radical polymerization. The resulting amphiphilic star-block copolymers could self-assemble into spherical micelles in water.

    30. Ionic liquids as novel solvents and catalysts for the direct polycondensation of N,N′-(4,4′-oxydiphthaloyl)-bis-L-phenylalanine diacid with various aromatic diamines (pages 6545–6553)

      Shadpour Mallakpour and Elaheh Kowsari

      Version of Record online: 1 NOV 2005 | DOI: 10.1002/pola.21100

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      Ionic liquids (ILs) are often considered green solvents capable of replacing traditional organic solvents and have been extensively studied in materials chemistry and catalysis. In this study, the direct polycondensation of N,N′-(4,4′-oxydiphthaloyl)-bis-L-phenylalanine diacid with various aromatic diamines was performed in IL media. The influence of various reaction parameters, including the nature of the IL cations and anions, the monomer structures, the reaction temperature, and the reaction time, on the yields and inherent viscosities of the resulting optically active poly-(amide imide)s (PAIs) were investigated.

    31. Synthesis and optical and electrochemical properties of new π-conjugated 1,3,5-triazine-containing polymers (pages 6554–6561)

      Shijie Ren, Qiang Fang, Feng Yu and Dongsheng Bu

      Version of Record online: 1 NOV 2005 | DOI: 10.1002/pola.21091

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      Two new π-conjugated polymers containing 1,3,5-triazine units in the main chain, Pa and Pb, are reported. Pa and Pb (R = H and [BOND]OCH3, respectively) showed blue photoluminescence emissions with quantum yields of more than 50% in toluene. In the solid state, Pa and Pb showed photoluminescence maximum emission peaks at 479 and 475 nm, respectively. Electrochemically, Pa and Pb showed good stability and reversibility under repeated electrochemical reduction. The polymers had glass-transition temperatures higher than 90 °C and had 5 wt % loss temperatures higher than 400 °C.

    32. Preparation of a reflective-type electrochromic device based on monodisperse, micrometer-size-range polymeric microspheres and viologen pendants (pages 6562–6572)

      Jee-Hyun Ryu, Dong-Oh Shin and Kyung-Do Suh

      Version of Record online: 1 NOV 2005 | DOI: 10.1002/pola.21131

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      A reflective electrochromic device (ECD) was prepared through the mixing of viologen-modified polymeric microspheres and an electrolyte and sandwiching with indium tin oxide glasses. Most of the conventional viologen-based ECDs were a transmissive type; for instance, viologen molecules were dissolved in the electrolyte or deposited on the electrode like a film. Therefore, an additional white reflector was needed for a reflective-type display. Our ECD system had an inherent white background because of the close packing of the polymer particles, and the fabrication process was very simple, combining the particles with the electrolyte.

    33. Novel fluorinated stabilizers for ring-opening polymerization in supercritical carbon dioxide (pages 6573–6585)

      Daniel Bratton, Malcolm Brown and Steven M. Howdle

      Version of Record online: 1 NOV 2005 | DOI: 10.1002/pola.21117

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      A series of novel fluorinated diblock copolymers based on Krytox 157 FSL and polycaprolactone were synthesized and assessed as stabilizers for ring-opening polymerization in supercritical carbon dioxide (scCO2). These copolymers successfully stabilized the suspension polymerization of L-lactide and glycolide in scCO2 at low loading levels, and this makes them the most effective stabilizers yet designed.

    34. Improvement of the thermal stability of cluster-crosslinked polystyrene and poly(methyl methacrylate) by optimization of the polymerization conditions (pages 6586–6591)

      Yu Gao, Franz Rene Kogler and Ulrich Schubert

      Version of Record online: 1 NOV 2005 | DOI: 10.1002/pola.21137

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      The polymerization conditions for polystyrene and poly (methyl methacrylate) crosslinked by 0.5 mol % of the cluster Zr6O4(OH)4(methacrylate)12 were optimized by applying a step polymerization procedure. This increases the thermal stability, the char yield, and the glass transition temperatures of the hybrid polymers.

    35. Oxidation polymerization of a charge-transfer complex of 2,6-bis(2-thienyl)-1,4-dithiafulvene with 7,7,8,8-tetracyanoquinodimethane (pages 6592–6598)

      Adriana Gelover-Santiago, Kensuke Naka and Yoshiki Chujo

      Version of Record online: 1 NOV 2005 | DOI: 10.1002/pola.21136

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      A π-conjugated poly(α-dithienylen-dithiafulvene) (2) was obtained by the oxidation polymerization of 2,6-bis(2-thienyl)-1,4-dithiafulvene (1). When a solution of 1 in CHCl3 was added to a stirred solution of FeCl3 in CHCl3, only the low-molecular-weight product 2 was obtained. A higher molecular weight polymer (4) was obtained by the oxidation polymerization of a charge-transfer complex of 1 with 7,7,8,8-tetracyanoquinodimethane (compound 3). In contrast to 2, polymer 4 was readily soluble in dimethyl sulfoxide, dimethylformamide, and acetone and partially soluble in tetrahydrofuran and methanol and had a larger molecular weight (peak top molecular weight = 37,000).

  3. Rapid Communications

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    1. Ring-opening metathesis copolymerization behaviors of cyclooctene and norbornene bearing a five- or six-membered ring cyclic carbonate (pages 6599–6604)

      Tetsuo Hino, Naoto Inoue and Takeshi Endo

      Version of Record online: 1 NOV 2005 | DOI: 10.1002/pola.21124

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      Ring-opening metathesis copolymerizations (co-ROMPs) of norbornene derivatives bearing five- or six-membered ring cyclic carbonate and cyclooctene were carried out with a ruthenium catalyst under various polymerization conditions. All co-ROMPs smoothly gave the corresponding copolymers in good yields, and the lass-transition temperatures of the resulting polymers and the degrees of volume change during the copolymerizations were simultaneously controlled by the amount of the comonomer.

    2. Aluminum Schiff base catalysts derived from β-diketone for the stereoselective polymerization of racemic lactides (pages 6605–6612)

      Xuan Pang, Hongzhi Du, Xuesi Chen, Xiuli Zhuang, Dongmei Cui and Xiabin Jing

      Version of Record online: 1 NOV 2005 | DOI: 10.1002/pola.21108

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      Two aluminum Schiff base catalysts with the formula LAlEt [L = bis(benzoylacetone)trimethylenediimine (1) or bis(benzoylacetone)ethylenediimine (2)] were designed and synthesized for a comparison of their catalytic properties in the polymerization of racemic lactides. Single-crystal data of catalyst 1 confirmed its trigonal bipyramidal configuration with a five-coordinated aluminum atom in the center. These catalysts were shown to be highly active and stereoselective for the controlled ring-opening polymerization of racemic lactides.

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    1. You have free access to this content
      One-pot non-isocyanate synthesis of polyurethanes from bisepoxide, carbon dioxide, and diamine (pages 6613–6618)

      Bungo Ochiai, Shoko Inoue and Takeshi Endo

      Version of Record online: 1 NOV 2005 | DOI: 10.1002/pola.21103

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      The polyaddition of bis(cyclic carbonate), in situ prepared from bisepoxide and carbon dioxide, and diamine afforded poly(hydroxyurethane) quantitatively. The resulting poly(hydroxyurethane) could be converted in situ to polyurethanes bearing either ester or silyl ether groups in the side chains.

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