Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Journal of Polymer Science Part A: Polymer Chemistry

1 June 2008

Volume 46, Issue 11

Pages 3459–3875

  1. Highlights

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    2. Highlights
    3. Articles
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      Polymerization of oligo(ethylene glycol) (meth)acrylates: Toward new generations of smart biocompatible materials (pages 3459–3470)

      Jean-François Lutz

      Version of Record online: 24 APR 2008 | DOI: 10.1002/pola.22706

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      Oligo(ethylene glycol)-based (macro)monomers allow the synthesis of novel biocompatible macromolecules with promising stimuli-responsive properties. For instance, well-defined random copolymers of 2-(2-methoxyethoxy)ethyl methacrylate (MEO2MA) and oligo(ethylene glycol) methacrylate (OEGMA) exhibit a lower critical solution temperature (LCST) in aqueous solution, which can be precisely adjusted by varying the comonomer composition. For example, cloud points of either 32 °C, 37 °C or 39 °C were observed in pure water for copolymers possessing in average respectively 5, 8 or 10% of OEGMA units per chain. Thus, these polymers can be used for building a wide variety of modern materials such as biosensors, artificial tissues, smart gels for chromatography and drug carriers. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

  2. Articles

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    3. Articles
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    1. Nanocomposites derived from in situ grafting of linear and hyperbranched poly(ether-ketone)s containing flexible oxyethylene spacers onto the surface of multiwalled carbon nanotubes (pages 3471–3481)

      In-Yup Jeon, Loon-Seng Tan and Jong-Beom Baek

      Version of Record online: 24 APR 2008 | DOI: 10.1002/pola.22649

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      Nanocomposites were derived from in situ grafting of linear and hyperbranched poly(ether-ketone)s containing flexible oxyethylene spacers onto the surface of MWNT via “direct” Friedel-Crafts reaction as the polymer-forming and grafting reaction at the same time. The resultant nanocomposites are soluble in most strong acids. From SEM and TEM studies, the polymers were uniformly grafted onto the MWNT. Nanocomposites displayed improved thermo-oxidative stability when compared with those of corresponding PEK homopolymers.

    2. Photomediated crosslinking of cinnamated PDMS for in situ direct photopatterning (pages 3482–3487)

      Jianxin Chen, Andrew R. Vaino, Rosemary L. Smith and Scott C. Collins

      Version of Record online: 24 APR 2008 | DOI: 10.1002/pola.22653

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      A thin film of PDMS with pendant cinnamated groups is exposed to ultraviolet light (UV-B) through a quartz photomask. The cinnamated PDMS is crosslinked to become rigid in exposed areas while cinnamated PDMS in unexposed areas is washed away by solvent after developed. The structures of glass slide substrates (15 × 15 μm, diamond squares in the picture) are fabricated in this method.

    3. A polarity-activation strategy for the high incorporation of 1-alkenes into functional copolymers via RAFT copolymerization (pages 3488–3498)

      Jun Ma, Chong Cheng, Guorong Sun and Karen L. Wooley

      Version of Record online: 24 APR 2008 | DOI: 10.1002/pola.22682

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      A new synthetic methodology for the preparation of copolymers having high incorporation of 1-alkene together with polar, reactive repeat units has been developed by polarity-activated RAFT copolymerization. This approach provides well-defined alternating poly(1-decene-alt-maleic anhydride), expanding the monomer types for living copolymerizations. Ternary copolymers with higher conversion of 1-decene could also be obtained by using additive amounts (5 mol %) of vinyl acetate or styrene.

    4. Atom transfer radical polymerization of hexyl acrylate and preparation of its “all-acrylate” block copolymers (pages 3499–3511)

      Haimanti Datta and Nikhil K. Singha

      Version of Record online: 24 APR 2008 | DOI: 10.1002/pola.22683

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      An in depth study was carried out on atom transfer radical polymerization (ATRP) of hexyl acrylate in bulk as well in solvents with varying polarity, using CuBr/PMDETA catalytic systems. UV-Vis analysis showed that the polar solvent acetone coordinated with copper (I), thereby influencing the dynamic equilibrium of activation–deactivation cycle. Monofunctional as well as difunctional polyhexyl acrylates were prepared and were used as acroinitiators to synthesize various block copolymers (diblock, triblock) using methyl methacrylate as comonomer.

    5. Thermally curable polyvinylchloride via click chemistry (pages 3512–3518)

      Baris Kiskan, Güniz Demiray and Yusuf Yagci

      Version of Record online: 24 APR 2008 | DOI: 10.1002/pola.22685

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      Novel side-chain benzoxazine functional polyvinylchloride (PVC-Benzoxazine) was synthesized by using “Click Chemistry” strategy. First, approximately 10% of chloro groups of polyvinylchloride (PVC) were converted to azido groups by using NaN3 in DMF. Propargyl benzoxazine was prepared independently by a ring closure reaction between p-propargyloxy aniline, paraformaldehyde, and phenol. Finally, azidofunctionalized PVC was coupled to propargyl benzoxazine with high efficiency by click chemistry. The spectral and thermal analysis confirmed the presence of benzoxazine functionality in the resulting polymer. It is shown that PVC containing benzoxazine undergoes thermally activated curing in the absence of any catalyst forming PVC thermoset with high thermal stability.

    6. Effect of coinitiator type on initiation efficiency of two-component photoinitiator systems based on Eosin (pages 3519–3532)

      Roman Popielarz and Otmar Vogt

      Version of Record online: 25 APR 2008 | DOI: 10.1002/pola.22688

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      Fluorescent probe technique (FPT) has been applied for optimization of initiation efficiency of two-component Eosin/coinitiator systems, used for photopolymerization of coatings formulations with visible light. A series of coinitiators have been tested in combination with Eosin, and their relative initiation efficiency has been evaluated quantitatively. The effects of structural features of the coinitiator and the initiation mechanism, on initiation efficiency of the systems studied are discussed. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    7. Hydrophilic graft modification of a commercial crystalline polyolefin (pages 3533–3545)

      Jihoon Shin, Andrew Y. Chang, Lacie V. Brownell, Ira O. Racoma, Coreen H. Ozawa, Ho-Yong Chung, Shufu Peng and Chulsung Bae

      Version of Record online: 25 APR 2008 | DOI: 10.1002/pola.22689

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      Hydroxy-functionalized isotactic poly(1-butene) was synthesized using transition metal-catalyzed regioselective C[BOND]H borylation at the side chain of the commercial polyolefin and subsequent oxidation of the boronic ester functionality. Controlled functionalization up to ∼ 19 mol % of the termini of the ethyl side chain occurred without significant side reactions that could alter the polymer chain length. Atom transfer radical polymerization of tert-butyl acrylate from a macroinitiator derived from the hydroxy-functionalized polymer and subsequent hydrolysis of the tert-butoxy ester group of the graft copolymer created an amphiphilic polyolefin, isotactic poly(1-butene)-graft-poly(acrylic acid). [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    8. Functionalization of surface-grafted polymethylhydrosiloxane thin films with alkyl side chains (pages 3546–3562)

      Thierry Thami, Gihane Nasr, Hanan Bestal, Arie Van Der Lee and Bruno Bresson

      Version of Record online: 25 APR 2008 | DOI: 10.1002/pola.22691

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      Surface-attached thin films of a polymethylhydrosiloxane (PMHS) network were deposited by a room-temperature sol–gel process and were thereafter functionalized by hydrosilylation of the SiH groups with 1-alkenes CH2[DOUBLE BOND] CH(CH2)n-2CH3. Postfunctionalization of PMHS gives a polysiloxane network with n-alkyl side chains. The influence of structural factors on the extent of SiH functionalization, such as the size of the alkenes and the mesh size of the network, was studied in relation to the crosslinking ratio. We obtained effective quantitative conversion of SiH within the 5% crosslinked PMHS network. The functionalized networks show crystallization of the long n-alkyl side chains. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    9. Fabrication of poly(aniline-co-pyrrole) hollow nanospheres with Triton X-100 micelles as templates (pages 3563–3572)

      Chuanqiang Zhou, Jie Han, Genping Song and Rong Guo

      Version of Record online: 25 APR 2008 | DOI: 10.1002/pola.22695

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      Poly(aniline-co-pyrrole) copolymer hollow nanospheres have been fabricated by the oxidation polymerization of a mixture of aniline and pyrrole in the presence of surfactant Triton X-100. The effects of experimental parameters, such as concentrations of surfactant and co-monomers, and [pyrrole]/[aniline] ratios, on the size and uniformity of copolymer hollow spheres were investigated in detail, and the formation mechanism was also discussed in this report. FTIR, UV–visible, 1H NMR, and XRD technologies have been employed to confirm the chemical structures and crystallinity of product, respectively. The thermal-stability and solubility of copolymer were found to be obviously improved compared with homopolymers (polyaniline and polypyrrole).

    10. Alternating fluorene copolymers containing isothianaphthene derivatives: A study of their aggregation properties and small band gap (pages 3573–3590)

      Young Kwan Jung, Hyoseok Kim, Jong-Hwa Park, Jaemin Lee, Sang Kyu Lee, Yoon Sup Lee and Hong-Ku Shim

      Version of Record online: 25 APR 2008 | DOI: 10.1002/pola.22696

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      We have synthesized five fluorene-based copolymers containing an isothianaphthene unit and similar moieties. P1 and P2 show very low PL intensities in the film state, which can be attributed to the aggregation of the polymers. Among these polymers, P2 shows the smallest band gap of 1.85 eV due to the extension of conjugation length resulting from the existence of isothianaphthene and selenophene units. Our results based on the optical and electrochemical properties combined with theoretical calculations showed that polymers containing isothianaphthene have small band gaps, rigid conformations, and strong tendencies to aggregation.

    11. Electro-optical behavior of ferroelectric liquid crystalline polyphenylene derivatives (pages 3591–3610)

      Kiyoshi Suda and Kazuo Akagi

      Version of Record online: 25 APR 2008 | DOI: 10.1002/pola.22698

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      We demonstrated that ferroelectric LC poly(para-phenylene) and poly(meta-phenylene) derivatives newly synthesized showed quick response to electric field to give dynamic switching in macroscopic alignment through polarization inversion, and the latter also showed stable memory function owing to large residual polarization.

    12. Real-time FTIR monitoring of the mechanism of initiation of isobutylene polymerizations by epoxide/Lewis acid systems (pages 3611–3618)

      Serap Hayat Soytaş, Judit E. Puskas and Kevin Kulbaba

      Version of Record online: 25 APR 2008 | DOI: 10.1002/pola.22699

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      The polymerization of isobutylene (IB) initiated by epoxide/BCl3 and TiCl4 initiating systems were investigated using real-time FTIR. Ring opening by TiCl4 was dominated by SN2 mechanism, while BCl3 facilitated the SN1 pathway. 2-epoxi-2,4,4-trimethylpentane with excess BCl3 yielded a telechelic PIB carrying α-primary OH and ω-tertiary Cl functionalities with 70% initiator efficiency.

    13. Impact of the clay organic modifier on the morphology of polymer–clay nanocomposites prepared by in situ free-radical polymerization in emulsion (pages 3619–3628)

      Nagi Greesh, Patrice C. Hartmann, Valeska Cloete and Ronald D. Sanderson

      Version of Record online: 25 APR 2008 | DOI: 10.1002/pola.22701

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      Poly(styrene-co-butyl acrylate)–clay nanocomposites were synthesized by free radical polymerization in emulsion, using 10% of clay surface modified with various surface modifiers. The morphology of the nanocomposites obtained (i.e. intercalated, partially exfoliated, or fully exfoliated) was found to be strongly dependent on the chemical structure of the clay modifier, its degree of interaction with clay, and its ability to copolymerize with the monomers. Accordingly, due to the difference in their morphologies, the thermal stability and thermomechanical properties of the nanocomposites were found to be significantly dependent on the type of the clay modifier used. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    14. Thermogelling behaviors of poly(caprolactone-b-ethylene glycol-b-caprolactone) triblock copolymer in the presence of hyaluronic acid (pages 3629–3637)

      In Yong Kim, Mi Kyong Yoo, Bom Chol Kim, In Young Park, Hyun Chul Lee and Chong Su Cho

      Version of Record online: 25 APR 2008 | DOI: 10.1002/pola.22702

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      Schematic representation of gelation mechanism by micellar aggregation of PCL-PEG-PCL micelles in the presence of HA. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    15. Kinetics of dispersion polymerization: Effect of medium composition (pages 3638–3647)

      Sheng Jiang, E. David Sudol, Victoria L. Dimonie and Mohamed S. El-Aasser

      Version of Record online: 25 APR 2008 | DOI: 10.1002/pola.22704

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      Varying the monomer concentration (MMA) in a dispersion polymerization affects the solvency of the medium (MMA/methanol/water) which in turn affects the nucleation process. The final particle size can decrease and then increase with increasing initial monomer concentration as seen here and the products can become polydisperse. The solvency affects the nucleation process by affecting both the stabilizer (PVP K-30 in this case) and the polymer (PMMA) precipitating from the medium.

    16. ROMP based photoinitiator-coinitiator systems with improved migration stability (pages 3648–3661)

      Martina Sandholzer, Monika Schuster, Franz Varga, Robert Liska and Christian Slugovc

      Version of Record online: 25 APR 2008 | DOI: 10.1002/pola.22705

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      Nowadays, migration stability is one of the key features for photoinitiators used in radiation curable formulations, especially when the material is in contact with food or the human body. Herein, the synthesis and characterization of statistical copolymers with covalently bound eosin and/or ethyl dimethylamino benzoate units by ring opening metathesis polymerization is presented. The prepared compounds were tested as macroinitiators for the photopolymerization of acrylates aiming at an initiator/co-initiator system which combines good polymerization activity with improved migration stability. An acrylate modified eosin derivative which is incorporated into the polymer network during the photopolymerization reaction and, therefore, less likely to leak from the polymer compound was used as reference. Photoinitiating activities of low and high molecular weight initiators and co-initiators were investigated by photo-DSC. Moreover, leakage studies and viability tests with osteoblast-like cells were performed in order to proof the suitability of this concept. The use of polymeric eosin in combination with a low molecular weight co-initiator was found to be a good compromise when aiming at a photo initiating system with sound performance and improved migration stability. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    17. Carbohydrate-based amphiphilic diblock copolymers: Synthesis, characterization, and aqueous properties (pages 3662–3672)

      Fabian Suriano, Olivier Coulembier, Philippe Degée and Philippe Dubois

      Version of Record online: 25 APR 2008 | DOI: 10.1002/pola.22707

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      Our investigation reports on the self-assembly of new amphiphilic block copolymers containing pendant sugars in the hydrophilic corona. Those were obtained by a controlled synthesis via a four-step strategy leading to well-defined copolymers in terms of structure and molecular characteristics. As exemplified by AFM and DLS such new architectures are able to aggregate in solution giving birth to spherical and monomodal micelles. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    18. Thermally latent reaction of hemiacetal ester with epoxide catalyzed by recyclable polymeric catalyst consisting of salen-zinc complex and polyurethane main chain (pages 3673–3681)

      Hiroyuki Komatsu, Bungo Ochiai and Takeshi Endo

      Version of Record online: 25 APR 2008 | DOI: 10.1002/pola.22708

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      This article describes synthesis of and catalysis with a polymeric catalyst (Zn/1NHCOO) carrying salen-zinc complex structure in the main chain prepared from polyaddition of zinc/bis(4-hydroxy)salicylidene-1,2-diiminoethane and 4,4′-diphenylmethane diisocyanate. Poly(Zn/1NHCOO) promoted the reaction of glycidyl phenyl ether (2) with1-propoxyethyl-2-ethylhexanoate (3) only at moderately elevated temperatures. Poly(Zn/1NHCOO) can be recycled by simple filtration from the reaction mixtures, and the recycled polymer is asactive as the freshly prepared one.

    19. Thermally latent synthesis of networked polymers from multifunctional hemiacetal ester and diepoxide catalyzed by Schiff-base-zinc chloride complex (pages 3682–3689)

      Hiroyuki Komatsu, Bungo Ochiai and Takeshi Endo

      Version of Record online: 25 APR 2008 | DOI: 10.1002/pola.22709

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      Thermally latent reaction of a copolymer (P1) bearing hemiacetal ester and n-butyl methacrylate moieties and bisphenol A diglycidyl ether (7) was catalyzed by bis(p-methoxybenzylidene)-1,2-diiminoethane/zinc chloride complex (ZnCl2/3) at 30–150 °C for 6 h. No reaction of P1 and 7 took place below 70 °C, whereas it smoothly proceeded above 120 °C.

    20. Synthesis of chiral micelles and nanoparticles from amino acid based monomers using RAFT polymerization (pages 3690–3702)

      Jared Skey and Rachel K. O'reilly

      Version of Record online: 25 APR 2008 | DOI: 10.1002/pola.22710

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      Optically active amphiphilic diblock copolymers, which contain chiral amino acid moieties within the hydrophobic block, were prepared by RAFT polymerization and then self-assembled to afford spherical micelles which were subsequently cross-linked throughout the shell layer to afford robust well-defined chiral nanoparticles. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    21. Polyfluorenes minimally doped with 1,4-bis(2-thienyl-2-cyanovinyl)benzene chromophore: Their synthesis, characterization, and application to white-light-emitting materials (pages 3703–3713)

      Bar-Yuan Hsieh and Yun Chen

      Version of Record online: 25 APR 2008 | DOI: 10.1002/pola.22711

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      Copolyfluorenes chemically doped with 0.1 (PFR1) and 0.025 mol % (PFR2) 2,5-dihexyloxy-1,4-bis(2-thienyl-2-cyanovinyl) benzene (MR chromophere) were synthesized by the Suzuki coupling reaction. The PFRs were attempted to fabricate white-light-emitting devices through incomplete energy transfer between the fluorene and MR moieties. The EL device [ITO/PEDOT:PSS/PFR2/Ca (50 nm)/Al (100 nm)] showed broad emission band, and its chromaticity coordinate was (0.32, 0.30), which is very close to pure white light. The maximal luminance and current efficiency were 3011 cd/m2 and 1.98 cd/A, respectively.

    22. An efficient solid-state polycondensation method for synthesizing stereocomplexed poly(lactic acid)s with high molecular weight (pages 3714–3722)

      Kazuki Fukushima and Yoshiharu Kimura

      Version of Record online: 25 APR 2008 | DOI: 10.1002/pola.22712

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      Stereoblock-type poly(lactic acid) is produced by solid-state polycondensation of the powder-blends of poly(L-lactic acid) and poly(D-lactic acid). The polycondensation is conducted below melting temperature of homo-chiral polymers so that chain extension reaction predominantly proceeds between homo-chiral chains to afford high molecular weight and significantly long L- and D-lactate sequences. Transesterfication in the minor stereocomplex domain resulting from partial fusion of powders provides a few junctions of L- and D-lactate sequences as well as random sequences. Exclusive stereocomplexation is triggered by melt crystallization of the final polycondensates which preferentially form homochiral polymer crystals. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    23. A new donor-acceptor type polymeric material from a thiophene derivative and its electrochromic properties (pages 3723–3731)

      Yasemin Arslan Udum, Ersin Yildiz, Gorkem Gunbas and Levent Toppare

      Version of Record online: 25 APR 2008 | DOI: 10.1002/pola.22713

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      A new highly stable electrochromic polymer, PTTQ was synthesized and its electrochromic properties were investigated In addition to its high stability, the polymer achieves an outstanding optical contrast of 98% in NIR region only in 0.6 s which is the highest NIR transmittance ratio in the literature with a switching time of less than 1 s making this polymer a paramount nominee for NIR device applications. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    24. Syntheses of multicyclic poly(ether sulfone)s from 5,5′,6,6′-tetrahydroxy-3,3,3′,3′-tetramethyl spirobisindane and 4,4′-bis(4-chlorophenyl) sulfones (pages 3732–3739)

      Hans R. Kricheldorf and Kirstin Bornhorst

      Version of Record online: 25 APR 2008 | DOI: 10.1002/pola.22714

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      Polycondensations of 5,5,6,6,-tetrahydroxyspirobisindane with 4,4′-bis(4-chlorophenyl sulfonyl) biphenyl gave high yields of perfect multicyclic polyethers, whereas analogous polycondensations with 4,4′-dichlorodiphenyl sulfone were for steric reasons less successful.

    25. RAFT synthesis of amphiphilic (A-ran-B)-b-C diblock copolymers with tunable pH-sensitivity (pages 3740–3748)

      Ying Qian Hu, Min Sang Kim, Bong Sup Kim and Doo Sung Lee

      Version of Record online: 25 APR 2008 | DOI: 10.1002/pola.22717

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      pH-responsive (A-ran-B)-b-C (A: 2-(diisopropylamino)ethyl methacrylate (DPA); B: 2-(diethylamino)ethyl methacrylate (DEA); C: N-(2-hydroxypropyl) methacrylamide (HPMA)) diblock copolymers were synthesized by RAFT process. Their pKb values varied linearly with the composition of A-ran-B part, regardless of the block length of HPMA and thus the tunability of their pH-sensitivity could be achieved. The fluorescence spectroscopy and dynamic light scattering evaluation confirmed the controllability of the pH-induced micellization behavior. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    26. Homogeneous anionic PPE hybrids with silica gel (pages 3749–3755)

      Kenta Kokado and Yoshiki Chujo

      Version of Record online: 25 APR 2008 | DOI: 10.1002/pola.22719

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      Anionic poly(p-phenylene-ethynylene) (PPE) incorporated polymer hybrids were synthesized. Up to 10 wt % of the anionic PPE could be dispersed homogeneously in the resulting polymer hybrid matrix. Furthermore, the photoluminescence of the obtained organic-inorganic polymer hybrids was also tuned by utilizing ionic interactions between the anionic PPE and the inorganic matrix. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    27. Controlled radical polymerization of N-vinylcaprolactam mediated by xanthate or dithiocarbamate (pages 3756–3765)

      Decheng Wan, Qing Zhou, Hongting Pu and Genjin Yang

      Version of Record online: 25 APR 2008 | DOI: 10.1002/pola.22722

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      The radical polymerization of NVCL could be controlled in the presence of CTA1-CTA3 via RAFT/MADIX process, with the controllability in the order of CTAI ≈ CTA2 < CTA3, MALDI-TOF analysis showed the polymerization was controlled, with typical PDI on the order of 1.24, but it is not an ideal RAFT/MADIX process.

    28. Photopolymerization kinetics of tributylmethylammonium-based (meth)acrylate ionic liquids and the effect of water (pages 3766–3773)

      Hui Zhou, Zulma Jiménez, John A. Pojman, Mark S. Paley and Charles E. Hoyle

      Version of Record online: 28 APR 2008 | DOI: 10.1002/pola.22723

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      Polymerizable ionic liquids formed from tributylmethyl ammonium hydroxide and (meth)acrylic acid.

    29. Dansylated acrylic copolymer with potential for sensor applications: Synthesis and properties (pages 3774–3782)

      Emil C. Buruiana, Mirela Zamfir and Tinca Buruiana

      Version of Record online: 28 APR 2008 | DOI: 10.1002/pola.22725

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      A copolymer containing 1,5-dimethylaminonaphtalene sulfonamide units was synthesized to investigate the photophysical properties in dilute solutions and in the presence of different quenchers of proton donor type, as 1(R)/(S)-camphorsulfonic acid, p-toluenesulphonic acid, HCl, 2-(methacryloyloxy)ethyl phosphate. Analysis of the quenching data in terms of the Stern-Volmer model sustains that an efficient quenching occurred through electronic energy transfer from the fluorescent-excited state of the protonated units to the ground state of the unprotonated ones.

    30. Photopolymerization with microscale resolution: Influence of the physico-chemical and photonic parameters (pages 3783–3794)

      Olivier Soppera, Safi Jradi and Daniel J. Lougnot

      Version of Record online: 28 APR 2008 | DOI: 10.1002/pola.22727

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      Influence of the dye concentration on the spatial extend of the photopolymerization. Left: photos taken after a 80 ms exposure showing the fluorescence images inside the drop during the fabrication process. Right: the corresponding polymer tips obtained after rinsing. The internal filter is used here to provide confinement of the photopolymerization. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    31. Pressure-induced polymerization of tetraethylene glycol dimethacrylate (pages 3795–3801)

      Kamil Kaminski, Marian Paluch, R. Wrzalik, Jerzy Ziolo, Radoslav Bogoslovov and C. Michael Roland

      Version of Record online: 28 APR 2008 | DOI: 10.1002/pola.22728

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      Results from the swelling experiments show clearly that polymerization of TEGDMA at high pressure is accompanied by substantial crosslinking. A plateau is reached at ∼12% conversion, with an increasing crosslink density reflected in the reduced degree of swelling. There is a significant increase in the extent of reaction with increasing the temperature, as expected.

    32. Synthesis and characterization of a series of biodegradable and biocompatible PEG-supported poly(lactic-ran-glycolic acid) amphiphilic barbell-like copolymers (pages 3802–3812)

      De Dai Lu, Jian Chao Yuan, Hongguang Li and Zi-Qiang Lei

      Version of Record online: 28 APR 2008 | DOI: 10.1002/pola.22729

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      A series of multi-hydroxyl end-groups poly(ethylene glycol) (PEG) was prepared from PEG and epichlorohydrin. Then the PEG-supported poly(lactic-ran-glycolic acid) (PLGA)n-PEG-(PLGA)n (n ¼ 1, 2, 4) linear-dendritic barbell-like copolymers were synthesized through direct polycondensation under bulk condition from the multi-hydroxyl endgroups PEG, lactic acid and glycolic acid. Arm numbers were varied, with 2, 4 and 8, by using bis-, tetra-, and octahydroxyl end-groups PEG, respectively.

    33. Dispersion copolymerization of 2-ethylhexyl methacrylate and vinylbenzyl chloride and functional group conversions in a fluorinated solvent using microwave heating (pages 3813–3819)

      Rangarani Karnati and Warren T. Ford

      Version of Record online: 28 APR 2008 | DOI: 10.1002/pola.22730

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      Microwave heating in the fluorinated solvent HFE-7200 of a dispersion polymerization of crosslinked poly(2-ethylhexyl methacrylate-co-vinylbenzyl chloride) and quaternization of the chloromethyl groups with trimethylamine produced stable colloidal dispersions, while in both cases oil bath heating produced coagulum.

    34. Benzophenothiazine and benzophenoxazine photosensitizers for triarylsulfonium salt cationic photoinitiators (pages 3820–3829)

      James V. Crivello

      Version of Record online: 28 APR 2008 | DOI: 10.1002/pola.22731

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      Benzophenothiazine and benzophenoxazine compounds are effective electron-transfer photosensitizers for triarylsulfonium salt cationic photoinitiators at wavelengths in the 400-500 nm spectral region. A number of these compounds were prepared and employed for the photosensitization of several different types of triarylsulfonium salts. The photosensitized vinyl and ring-opening polymerizations of several types of vinyl and heterocyclic monomers were conducted and the results are reported in this communication.

    35. Synthesis of a new zirconium catalyst for ethylene polymerization (pages 3830–3841)

      Fabiana De C. Fim, Tiago Machado, Denise Santos De Sá, Paolo R. Livotto, Zênis N. Da Rocha, Nara R. De S. Basso and Griselda Barrera Galland

      Version of Record online: 28 APR 2008 | DOI: 10.1002/pola.22734

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      A novel complex the dichlorobis(2-ethyl-3-hydroxy-4-pyrone)zirconium(IV) (ZrCl2(ethylpyrone)2) was synthesized. NMR showed the presence of four isomers and DFT calculations indicated that the main one has the chlorine atoms in cis. The complex is active in ethylene polymerization in the presence of methylaluminoxane. Electrochemical studies results showed that the nature of the alkyl group (methyl or ethyl) in the pyrone ring has no influence in the electronic density of Zr(IV) and that the active specie is stabilized by ethylene atmosphere.

    36. Polyion complex micelles formed from glucose oxidase and comb-type polyelectrolyte with poly(ethylene glycol) grafts (pages 3842–3852)

      Akifumi Kawamura, Chie Kojima, Michihiro Iijima, Atsushi Harada and Kenji Kono

      Version of Record online: 28 APR 2008 | DOI: 10.1002/pola.22739

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      Glucose oxidase was successfully entrapped into the core of polyion complex micelles through the complexation with the comb-type polyelectrolyte, poly(ethylene glycol)-g-poly (allyl amine), and maintained its enzymatic activity even in the core of micelles. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

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      Interactions of ionic liquids with polysaccharides. IV. Dendronization of 6-azido-6-deoxy cellulose (pages 3853–3859)

      Thomas Heinze, Michael Schöbitz, Matthias Pohl and Frank Meister

      Version of Record online: 28 APR 2008 | DOI: 10.1002/pola.22697

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      The conversion of 6-azido-6-deoxy cellulose (degree of substitution, DS 0.75) homogeneously in the ionic liquid 1-ethyl-3-methylimidazolium acetate with polyamidoamine (PAMAM) dendrons possessing an ethynyl focal moiety via the copper catalyzed Huisgen reaction (“click” reaction) yielded a novel biopolymer derivative. First to third generation PAMAM-triazolo-cellulose derivatives with DS values of up to 0.60 could be prepared, which are soluble in DMSO and for the third generation even in water. The cellulose derivatives were characterized by elemental analysis, FTIR and NMR spectroscopic methods showing neither remaining ionic liquid and other impurities nor conversion at secondary positions.

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      Ionomers for proton exchange membrane fuel cells with sulfonic acid groups on the end-groups: Novel branched poly(ether-ketone)s with 3,6-ditrityl-9H-carbazole end-groups (pages 3860–3868)

      Sumiko Matsumura, Antisar R. Hlil, Naiying Du, Catherine Lepiller, Julie Gaudet, Daniel Guay, Zhiqing Shi, Steven Holdcroft and Allan S. Hay

      Version of Record online: 28 APR 2008 | DOI: 10.1002/pola.22690

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      Branched wholly aromatic poly(ether-ketone)s (PEKs) bearing clusters of sulfonic acid groups on a novel end-group, 3,6-ditrityl-9H-carbazole, were synthesized by the polycondensation of activated aromatic difluorides and 4,4′-dihydroxybenzophenone in the presence of the above end-group and trifunctional branching agent, 1,3,5-tris(4-(4-fluorophenylsulfonyl)phenyl)benzene, followed by postsulfonation to introduce up to 8 sulfonic acid groups on each endgroup in PEKs. PEMs of these sulfonated branched PEKs with the same level of IECs (0.99–1.25 mequiv./g) as Nafion® (0.91 mequiv./g) showed proton conductivities (66–95 mS/cm) comparable to that (98 mS/cm) of Nafion®®. TEM analysis showed significantly phaseseparated, and worm-like, highly connected morphology in the PEK membranes.

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      Polystyrene star-shaped polymers containing core built from diepoxides (pages 3869–3875)

      Grzegorz Lapienis and Beata Wiktorska

      Version of Record online: 28 APR 2008 | DOI: 10.1002/pola.22733

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      Star-shaped polymers (AxBy(OH)x) were prepared by the reaction of commercial polystyrene (A), containing hydroxyl end groups (Mn ≈ 4700), with diglycidyl ether of neopentyl glycol (DGNG) (B). Polymers having Mn ≤ 400, 000 and number of arms (f) up to 75 were obtained. The structure of intermediate and final product was determined by 1H NMR and MALDI-TOF. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley. com.]

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