Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 47 Issue 22

15 November 2009

Volume 47, Issue 22

Pages 5929–6332

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      Hydrogels: From soft contact lenses and implants to self-assembled nanomaterials (pages 5929–5946)

      Jindrich Kopecek

      Version of Record online: 6 OCT 2009 | DOI: 10.1002/pola.23607

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      Hydrogels were the first biomaterials designed for clinical use. Historically, cross-linked polymers of hydrophilic esters and substituted amides of (meth)acrylic acid were used for contact lenses and tissue implants. Recent developments include advanced, stimuli-sensitive, drug delivery vehicles, with enhanced mechanical properties. In the last 10 years, hybrid hydrogels, composed of synthetic and natural components, such as coiled-coils and β-sheets, have also received significant interest in the field. Future research will continue on the development of hydrogels with programmable biofunctionality/ biocompatibility and self-assembly features. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

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    1. Star polymers with POSS via azide–alkyne click reaction (pages 5947–5953)

      Eda Gungor, Cigdem Bilir, Hakan Durmaz, Gurkan Hizal and Umit Tunca

      Version of Record online: 6 OCT 2009 | DOI: 10.1002/pola.23637

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      Azidopropyl-heptaisobutyl-substituted polyhedral oligomeric silsesquioxane (POSS-N3) was reacted with 1,1,1-tris[4-(2-propynyloxy)phenyl]-ethane (1) and poly(ethylene glycol) (PEG)-b-poly(methyl methacrylate) (PMMA) copolymer with alkyne at its center (PEG-PMMA-alkyne) affording the first time synthesis of 3-arm star POSS and PEG-PMMA-POSS 3-miktoarm star terpolymer, respectively, in the presence of CuBr/N,N,N′,N″,N″-pentamethyldiethylenetriamine as catalyst and N,N-dimethylformamide/tetrahydrofuran as solvent at room temperature.

    2. Poly(ethylene-co-1,4-cyclohexylenedimethylene terephthalate) copolyesters obtained by ring opening polymerization (pages 5954–5966)

      Nathalie González-Vidal, Antxon Martínez De Ilarduya and Sebastián Muñoz-Guerra

      Version of Record online: 6 OCT 2009 | DOI: 10.1002/pola.23639

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      Copolyesters of PET containing 1,4-cyclohexylenedimethylene terephthalate with controlled compositions and essentially random microstructure were prepared by ring-opening polymerization of cyclic oligomers obtained by cyclo-depolymerization of PET and PCT.

    3. Synthesis and self-assembly behavior of amphiphilic polypeptide-based brush-coil block copolymers (pages 5967–5978)

      Chunhua Cai, Wenjie Zhu, Tao Chen, Jiaping Lin and Xiaohui Tian

      Version of Record online: 6 OCT 2009 | DOI: 10.1002/pola.23640

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      Amphiphilic brush-coil block copolymers bearing hydrophilic PEG segment and hydrophobic polypeptide brush segment were synthesized. These copolymers were found to form spherical micelles, spindle-like micelles, and rod-like micelles in sequence, as the length of polypeptide brush increases. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    4. Synthesis and properties of through-space conjugated polymers based on cyano-substituted poly(p-arylenevinylene)s (pages 5979–5988)

      Yasuhiro Morisaki, Lin Lin and Yoshiki Chujo

      Version of Record online: 7 OCT 2009 | DOI: 10.1002/pola.23641

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      New through-space cyano-substituted poly(p-arylenevinylene)s containing a [2.2]paracyclophane unit were synthesized by the Knoevenagel reaction. Polymers 5 and 7 have cyano groups at α-positions and β-positions from the dialkoxyphenylene unit, respectively. Their optical and electrochemical behaviors were investigated in detail in comparison with their model compounds. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    5. Synthesis and characterization of thermoresponsive polymers containing reduction-sensitive disulfide linkage (pages 5989–5997)

      Lihua Li, Xulin Jiang and Renxi Zhuo

      Version of Record online: 6 OCT 2009 | DOI: 10.1002/pola.23642

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      Thermosensitive and reduction-responsive polymers p(PEG-MEMA-co-Boc-Cyst-MMAm)s were synthesized and characterized. These polymers can easily and quickly form stable nanoparticles by a quick heating process in neutral aqueous medium, but get rapidly destabilized in a reductive environment mimicking the intracellular space making them suitable for cytoplasmic drug delivery. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    6. Supramolecular assembly of H-bonded side-chain polymers containing conjugated pyridyl H-acceptor pendants and various low-band-gap H-donor dyes bearing cyanoacrylic acid groups for organic solar cell applications (pages 5998–6013)

      Tzung-Chi Liang, I-Hung Chiang, Po-Jen Yang, Dhananjay Kekuda, Chih-Wei CHU and Hong-Cheu Lin

      Version of Record online: 6 OCT 2009 | DOI: 10.1002/pola.23643

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      Novel supramolecular side-chain polymers were constructed by complexation of proton acceptor (H-acceptor) polymers, i.e., side-chain conjugated polymers P1–P2 containing pyridyl pendants, with low-band-gap proton donor (H-donor) dyes S1–S4 (bearing terminal cyanoacrylic acids) in a proper molar ratio. H-bonded polymer complexes P1/S1–P1/S4 and P2/S1–P2/S4 exhibited broad absorption peaks in the range of 440–462 nm with optical band-gaps of 2.11–2.25 eV. The PSC device containing H-bonded polymer complex P1/S3 blended with PCBM (1:1 w/w) gave the best preliminary result with an overall power conversion efficiency (PCE) of 0.50%, a short-circuit current of 3.17 mA/cm2, an open-circuit voltage of 0.47 V, and a fill factor of 34%. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    7. DNA binding to electropolymerized N-substituted polypyrrole surfaces (pages 6014–6024)

      Simona Percec, Gabriel Skidd and Ming Zheng

      Version of Record online: 6 OCT 2009 | DOI: 10.1002/pola.23644

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      N-substituted pyrrole monomers were electropolymerized under different conditions on gold working electrodes in a three-electrode/single compartment cell and on preselected electrode positions of the Molecular Nanosystems wafers. Subsequent DNA reactions were performed by incubating the resulting conductive films with amino-substituted DNA sequences. Conversely, it was determined that the electropolymerization reactions can be controlled and the conductive films are restricted to grow by electrically passivating the selected electrodes with self-assembled multilayers of hexadecane thiol. AFM, IR, and cyclic voltammetry were used to characterize the monomers, the polymers, and the attachment of the DNA to polypyrrole surfaces.

    8. Synthesis, characterization, and properties of polyurethanes containing 1,4:3,6-dianhydro-D-sorbitol (pages 6025–6031)

      Chi-Han Lee, Hideki Takagi, Hirotaka Okamoto, Makoto Kato and Arimitsu Usuki

      Version of Record online: 6 OCT 2009 | DOI: 10.1002/pola.23645

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      Polyurethanes containing 1,4:3,6-dianhydro-D-sorbital (isosorbide) were synthesized using n-BuSn([DOUBLE BOND]O)OHH2O as a catalyst. The polymers were soluble in organic solvents (DMSO, NMP) and had high Tg values. The storage modulus values (E′) of three components polymers were constant to a higher temperature than that of two components polymer. The thermal stabilities of three components polymers were also greater, with 5% weight loss temperature (Td) higher than that of two components, polymers, owing to the introduction of the bisphenol A and diphenylmethane groups.

    9. Well-defined amphiphilic graft copolymer consisting of hydrophilic poly(acrylic acid) backbone and hydrophobic poly(vinyl acetate) side chains (pages 6032–6043)

      Yaogong Li, Yaqin Zhang, Dong Yang, Chun Feng, Sujuan Zhai, Jianhua Hu, Guolin Lu and Xiaoyu Huang

      Version of Record online: 6 OCT 2009 | DOI: 10.1002/pola.23646

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      A series of well-defined amphiphilic graft copolymers containing hydrophilic poly(acrylic acid) backbone and hydrophobic poly(vinyl acetate) side chains were synthesized via sequential RAFT polymerization followed by selective hydrolysis of poly(tert-butyl acrylate) backbone. Grafting-from strategy was employed to synthesize PtBA-g-PVAc well-defined graft copolymers with narrow molecular weight distributions (Mw/Mn < 1.40). The critical micelle concentrations (cmc) of PAA-g-PVAc amphiphilic graft copolymers in aqueous media were determined by fluorescence probe technique. The micelle morphologies were found to be spheres. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    10. Reactive intermediates in the initiation step of the photo-oxidation of MDMO-PPV (pages 6044–6052)

      Sylvain Chambon, Agnès Rivaton, Jean-Luc Gardette and Muriel Firon

      Version of Record online: 7 OCT 2009 | DOI: 10.1002/pola.23628

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      We have investigated the reactive intermediates involved in the photoinitiated oxidation of poly[2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV). The results strongly evidenced that singlet oxygen is not the principal photo-oxidative degradation intermediate of MDMO-PPV. This result is in contradiction with previous reports. We have shown that the radical cation MDMO-PPV•+ was generated after excitation. Atmospheric oxygen and photodegradation products were shown to act as electron acceptors. Radical cations may react with oxygen, evolve by scission, and generate radicals that can enter the photo-oxidative degradation mechanism of MDMO-PPV by abstraction of labile hydrogen atoms of the polymer. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    11. Strongly electron deficient sulfonyldithioformate based RAFT agents for hetero Diels-Alder conjugation: Computational design and experimental evaluation (pages 6053–6071)

      Leena Nebhani, Sebastian Sinnwell, Ching Yeh Lin, Michelle L. Coote, Martina H. Stenzel and Christopher Barner-Kowollik

      Version of Record online: 7 OCT 2009 | DOI: 10.1002/pola.23647

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      The performance of strongly electron deficient sulfonyldithioformate based RAFT agents is evaluated with regard to their ability to impart living characteristics onto radical polymerizations as well as to react rapidly at ambient temperature with dienes to form polymer conjugates in click-type reactions.

    12. Living copolymerization of ethylene with norbornene mediated by heteroligated (Salicylaldiminato)(β-enaminoketonato)titanium catalysts (pages 6072–6082)

      Ying-Yun Long, Wei-Ping Ye, XIN-CUI SHI and Yue-Sheng Li

      Version of Record online: 7 OCT 2009 | DOI: 10.1002/pola.23648

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      A series of novel heteroligated (salicylaldiminato)(β-enaminoketonato)titanium catalysts were investigated as the catalysts for ethylene polymerization and ethylene/norbornene copolymerization in the presence of modified methylaluminoxane. When the norbornene concentration in the feed was higher than 0.4 mol/L, the heteroligated catalysts mediated the living copolymerization of ethylene with norbornene to form narrow molecular weight distribution copolymers (Mw/Mn < 1.20) under the mild conditions.

    13. Mechanism of cyclic dye regeneration during eosin-sensitized photoinitiation in the presence of polymerization inhibitors (pages 6083–6094)

      Heather J. Avens and Christopher N. Bowman

      Version of Record online: 7 OCT 2009 | DOI: 10.1002/pola.23649

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      Eosin (E) as a photosensitizer and N-methyldiethanolamine (MDEA) as a coinitiator initiate photopolymerization in the presence of 1000-fold excess oxygen or 100-fold excess 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) inhibitors relative to the eosin concentration. Through kinetic analysis of photoinitiation by eosin as compared to Irgacure 2959, a standard cleavage-type initiator, a mechanism is identified to explain eosin's ability to overcome polymerization inhibitors. The proposed mechanism posits that eosin radicals (E) react by disproportionation with radical inhibitors and radical intermediates (Inh) in the inhibition process to regenerate eosin and inactivate inhibitor (Inh*). Choice of certain dye photosensizers constitutes a valuable strategy to mitigate inhibition. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    14. Monitoring ultrathin film photopolymerization of tetra-alkylepoxyporphyrin by UV-Vis spectroscopy (pages 6095–6103)

      Kalle Lintinen, Linda Storbacka, Alexander Efimov, Sami Hietala, Risto Ahorinta, Nikolai Tkachenko and Helge Lemmetyinen

      Version of Record online: 7 OCT 2009 | DOI: 10.1002/pola.23650

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      We have synthesized and photopolymerized a highly viscous, cross-linking monomer, tetra-alkylepoxyporphyrin (TAEP). It is possible to monitor photopolymerization of ultrathin films by UV-Vis spectroscopy and compare the substrate effect on polymerization speed. Photopolymerization is only possible on extremely smooth and hydrophilic surfaces, such as plasma treated fused quartz. Polymerization can be initiated with either UV-light or visible light. It was found that TAEP works as a photosensitizer for cationic photopolymerization. The method is a mild and versatile technique for in situ preparation of thin polymeric films directly from chromophore monomers. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    15. Aminated PCL-based copolymers by chemical modification of poly(α-iodo-ε-caprolactone-co-ε-caprolactone) (pages 6104–6115)

      Sarah El Habnouni, Sébastien Blanquer, Vincent Darcos and Jean Coudane

      Version of Record online: 7 OCT 2009 | DOI: 10.1002/pola.23652

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      Poly(α-iodo-ε-caprolactone-co-ε-caprolactone) (poly(αIεCL-co-εCL)) was used as polymeric substrate to access to new aminated poly(ε-caprolactone)s. Random copolymers poly(αIεCL-co-εCL) were prepared by ring-opening polymerization of α-iodo-ε-caprolactone with ε-caprolactone, The aminated PCLs open the way to new cationic and water-soluble PCL-based polyesters. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    16. Synthesis and characterization of poly(fluorinated vinyl ether-alt-tert-butyl α-trifluoromethacrylate) copolymers (pages 6116–6123)

      Jean-Marc Cracowski, Véronique Montembault, Fabrice Odobel, Bruno Améduri and Laurent Fontaine

      Version of Record online: 7 OCT 2009 | DOI: 10.1002/pola.23653

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      Radical copolymerization of electron acceptor tert-butyl α-trifluoromethacrylate (MAF-TBE) and electron donor 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-10-(vinyloxy)decane (FAV8) initiated by tert-butyl 2,2-dimethylperoxypropanoate leads to soluble copolymers containing 60–65 mol % of MAF-TBE. The reactivity ratios determined by the Kelen-Tüdos method were found to be rMAF-TBE = 0.03 ± 0.01 and rFAV8 = 0 at 74 °C, indicating the synthesis of alternated copolymers. TGA analyses showed the release of isobutene from MAF-TBE units in copolymers before a degradation of the resulting poly(α-trifluoromethacrylic acid-alt-FAV8) copolymers, occurring at 250–260 °C.

    17. Patterned immobilization of biomolecules by using ion irradiation-induced graft polymerization (pages 6124–6134)

      Jae-Hak Choi, Ramakrishnan Ganesan, Dong-Ki Kim, Chan-Hee Jung, In-Tae Hwang, Young-Chang Nho, Je-Moon Yun and Jin-Baek Kim

      Version of Record online: 7 OCT 2009 | DOI: 10.1002/pola.23655

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      An efficient method for biomolecular patterning based on ion irradiation-induced graft polymerization has been demonstrated. Ion irradiation resulted in the formation of active species on the polymer surface, which in turn was utilized for graft polymerization of acrylic acid. Polymerization conditions were optimized to yield maximum grafting degree of poly(acrylic acid) onto the PTFE. The application of this platform for biomolecular patterning has been successfully demonstrated by patterning DNA and streptavidin on the poly(acrylic acid)-grafted PTFE substrates. This method is capable of grafting various functional groups such as amide and alcohol onto a variety of polymer substrates. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    18. Grafting of aldehyde structures to single-walled carbon nanotubes for application in phenolic resin-based composites (pages 6135–6144)

      Yehai Yan, Shuai Zhao, Jian Cui and Shaobei Yang

      Version of Record online: 7 OCT 2009 | DOI: 10.1002/pola.23656

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      Grafting of aldehyde structures to SWNTs has been carried out to endow the nanotubes with appropriate wettability. The improved wettability was demonstrated by good dispersion of aldehyde-functionalized SWNTs (f-SWNTs) in both ethanol and phenolica resin. The presence of aldehyde structures may also enhance the interfacial adhesion through covalent bonding between f-SWNT and phenolic resin. Phenolic resin/f-SWNT composite thus showed significant improvement of tensile strength in comparison with phenolic resin as well as composite filled with purified SWNTs. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    19. Immobilization of flame retardant onto silica nanoparticle surface and properties of epoxy resin filled with the flame retardant-immobilized silica (pages 6145–6152)

      Takeshi Yamauchi, Akira Yuuki, Gang Wei, Kumi Shirai, Kazuhiro Fujiki and Norio Tsubokawa

      Version of Record online: 7 OCT 2009 | DOI: 10.1002/pola.23657

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      Flame retardant, poly(2,2′,6,6′-tetrabromobisphenol-A) diglycidyl ether (PTBBA), was successfully immobilized to terminal amino groups of hyperbranched poly(amidoamine)-grafted silica nanoparticle (Silica-PAMAM). The immobilization of PTBBA was confirmed by FTIR spectra and thermal decomposition GC-MS. The amount of PTBBA immobilized onto Silica-PAMAM was determined to be 60 wt %. The LOI of epoxy resin filled with the PTBBA-immobilized Silica-PAMAM was higher than that filled with untreated silica and free PTBBA. The elimination of PTBBA from epoxy resin filled with Silica-PAMAM-PTBBA into boiling water was hardly observed. The results clearly show the anchor effect of silica nanoparticle for the immobilization of PTBBA.

    20. Synthesis and characterization of an ionic conjugated polymer: Poly[2-ethynyl-N-(2-thiophenecarbonyl) pyridinium chloride] (pages 6153–6162)

      Yeong-Soon Gal, Sung-Ho Jin, Jong-Wook Park and Kwon Taek Lim

      Version of Record online: 8 OCT 2009 | DOI: 10.1002/pola.23658

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      The activated polymerization of 2-ethynylpyridine by using 2-thiophenecarbonyl chloride yielded the corresponding conjugated ionic polymer, poly[2-ethynyl-N-(2-thiophenecarbonyl)pyridinium chloride] (PETCPC). The instrumental analysis data on polymer structure indicated that the present ionic polymer have a conjugated polymer backbone system having N-(2-thiophenecarbonyl)pyridinium as substituents. The photoluminescence maximum peak of polymer was located at 573 nm, which corresponds to the photon energy of 2.16 eV. The cyclovoltamograms of polymer exhibited the electrochemically stable window at −1.24 to 1.80 V region. The kinetics of the redox process of polymer was found to be controlled by the reactant diffusion process from the experiment of the oxidation current density of polymer versus the scan rate.

    21. Generation of radical species on polypropylene by alkylborane-oxygen system and its application to graft polymerization (pages 6163–6167)

      Hirokazu Okamura, Atushi Sudo and Takeshi Endo

      Version of Record online: 8 OCT 2009 | DOI: 10.1002/pola.23659

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      Graft polymerization of various acrylates such as ethyl acrylate and n-butyl acrylate onto polypropylene (PP) surface by borane-O2 redox system was investigated using different types of solvent and soaking time of PP beads in borane solution. The utilization of less polar solvent and longer soaking time are the two factors that would improve the efficiency of the grafting ratio. Glycidyl methacrylate (GMA) and acrylic acid were also grafted onto the PP surface. The PP surface endowed with poly(GMA) graft chains was reactive with amine, and it is potentially reactive with epoxy-amine-type adhesives that are used in wide variety of applications. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    22. Synthesis and thermoresponsive behaviors of biodegradable Pluronic analogs (pages 6168–6179)

      Yu-Cai Wang, Hai Xia, Xian-Zhu Yang and Jun Wang

      Version of Record online: 8 OCT 2009 | DOI: 10.1002/pola.23660

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      We synthesized biodegradable Pluronic analogs based on block copolymers of poly(propylene oxide) and poly(ethyl ethylene phosphate) (PEEP-PPO-PEEP). At higher concentration from 20 to 40 wt %, the aqueous solution of PEEP-PPOPEEP underwent thermo-induced phase transitions from a clear solution to a turbid solution, then to opaque gel and syneresis phases, depending on the molecular weights of PEEP blocks. To our knowledge, it was the first time to prepare polymers with a biodegradable hydrophilic block which has a thermo-induced sol-gel transition. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    23. PIB-based polyurethanes. IV. The morphology of polyurethanes containing soft co-segments (pages 6180–6190)

      Jungmee Kang, Gabor Erdodi, Joseph P. Kennedy, Emel Yilgor and Iskender Yilgor

      Version of Record online: 8 OCT 2009 | DOI: 10.1002/pola.23661

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      Novel polyurethanes comprising polyisobutylene (PIB)/poly-(tetramethylene oxide) (PTMO) or PIB/poly(hexamethylene carbonate) (PC) soft co-segments plus 4,4′-methylene-bis(cyclohexyl isocyanate) (HMDI)/1,6-hexanediol (HDO) hard segments exhibit upto 31 MPa tensile strength and 700% elongation, together with unprecedented oxidative/hydrolytic stability. Our morphological model proposes H bridges between the PTMO or PC soft and urethane hard segments that compatibilize soft and hard domains. Large quantities of chemically resistant PIB segments protect the oxidatively/hydrolytically vulnerable constituents. FTIR, DSC, SAXS, AFM, and DMTA experiments support the morphological model. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    24. Tri-block copolymers of polyethylene glycol and hyperbranched poly-3-ethyl-3-(hydroxymethyl)oxetane through cationic ring opening polymerization (pages 6191–6200)

      Martin Rahm, Robert Westlund, Carina Eldsäter and Eva Malmström

      Version of Record online: 8 OCT 2009 | DOI: 10.1002/pola.23662

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      Dumb-bell shaped tri-block copolymers of linear poly(ethylene glycol) (PEG) and hyperbranched poly-3-ethyl-3-(hydroxy methyl)oxetane (poly-TMPO) have been synthesized with cationic ring-opening polymerization using BF3OEt2. Crystallinity and melting point of the materials were tuned by varying the amount of poly-TMPO attached to the PEG-chains, from a melting point of 54 °C and a degree of crystallinity of 76% for pure PEG, to a melting point of 34 °C and a degree of crystallinity of 12% for the polyether having an average of 14 TMPO per PEG chain. The materials are of relatively low polydispersity, with Mn/Mw ranging from 1.2 to 1.4. Poly-TMPO is reported to be compatible with the energetic oxidizer ammonium dinitramide. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    25. Hydrazine-functionalized latexes (pages 6201–6213)

      Álvaro Costoyas, Jose Ramos and Jacqueline Forcada

      Version of Record online: 8 OCT 2009 | DOI: 10.1002/pola.23663

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      The noncommercial functional monomer 4-vinylbenzyl hydrazine (VBH) was synthesized and subsequently copolymerized with styrene (St) by means of different batch and semicontinuous seeded emulsion polymerization processes, so as to obtain hydrazine-functionalized nanoparticles. The effect of pH, surfactant and initiator amounts, ratio VBH/St, reaction temperature, and ratio acetone/water were studied. Due to the amphiphilic character of VBH at acid pH, the hydrazine groups of the functionalized comonomer were masked with acetone to form hydrazone groups. Secondary nucleations were avoided by using the protected VBH comonomer; however, a decreased radical efficiency achieving limited conversion was observed. Controlling the cationic initiator concentration, complete conversions together with the neat growth of the seed particles were obtained in the semicontinuous seeded emulsion polymerization of styrene and VBH protected with acetone.

    26. Ring opening insertion polymerization of ε-caprolactone with hydrogen phosphonate initiators (pages 6214–6222)

      Li J. Liu, Shao J. Cai, Ye Tan, Jiao J. Du, Hai Q. Dong, Xiao J. Wu, Ming Y. Wu and Li Q. Liao

      Version of Record online: 8 OCT 2009 | DOI: 10.1002/pola.23664

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      A ring opening insertion polymerization of ε-caprolactone (ε-CL) using a series of hydrogen phosphonates as initiators was investigated. ε-CL was activated first by the initiator such as, diisopropyl H-phosphonate (diiPro-HP) and the activated ε-CL was then inserted into the diiPro-HP to form the mono-CL-inserted diiPro-HP, which was still able to induce the ring opening of ε-CL and to be inserted by the thus activated ε-CL to form the poly(ε-caprolactone) (PCL)-inserted H-phosphonate. PCL with a number-average molar mass of 7800 g/mol was obtained after 60 min microwave irradiation (510 W). [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    27. Assembly of a fluorescent cyclodextrin polyrotaxane and its detection by fluorescence microscopy (pages 6223–6230)

      Gerhard Wenz, Iris Kräuter and Erich Sackmann

      Version of Record online: 8 OCT 2009 | DOI: 10.1002/pola.23666

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      A straightforward method for the assembly of fluorescent polyrotaxanes is described. The consecutive threading of a fluorescent β-CD derivative and α-CD onto the polymer ionene-6,10 in aqueous solution leads to a fluorescent polyrotaxane stable at 25 °C. Single polyrotaxane entities could be visualized through both fluorescence microscopy and atomic force microscopy.

    28. Synthesis and electroluminescent properties of polyfluorene-based conjugated polymers containing bipolar groups (pages 6231–6245)

      Sheng-Tung Huang, Der-Jang Liaw, Li-Ga Hsieh, Chin-Chuan Chang, Man-Kit Leung, Kun-Li Wang, Wen-Tung Chen, Kueir-Rarn Lee, Juin-Yih Lai, Li-Hsin Chan and Chin-Ti Chen

      Version of Record online: 8 OCT 2009 | DOI: 10.1002/pola.23667

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      A bipolar dibromo monomer containing donor and acceptor moieties was newly synthesized and characterized. Two fluorescent fluorene-based conjugated copolymers (TPAF, TPABTF) were prepared via facile Suzuki coupling from the bipolar monomer, 4,7-dibromo-2,1,3-benzothiadiazole (BTDZ), and 9,9-dioctylfluorene. Single layer polymer light-emitting diodes (PLED) of ITO/PEDOT:PSS/polymer/metal showed a blue emission at 444 nm for TPAF and at 542 nm for TPABTF. Introduction of the bipolar moiety on to the polyfluorene backbone would significantly help in balancing charge injection and transport through the polymer matrix. The electroluminescent properties of the polymers showed low turn-on voltages due to the bipolar moiety. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    29. Synthesis and characterization of photosensitive benzocyclobutene-functionalized siloxane thermosets (pages 6246–6258)

      Xiaobiao Zuo, Ruilian Yu, Song Shi, Zhihai Feng, Zhongping Li, Shiyong Yang and Lin Fan

      Version of Record online: 8 OCT 2009 | DOI: 10.1002/pola.23668

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      A novel series of benzocyclobutene-terminated siloxane monomers have been synthesized by the incorporation of phenyl groups on side chain, which were then converted to partially polymerized resins with high molecular weights at about 160–170 °C for different time. By combining these polymerized resins with BAC-M as a photosensitive agent, a negative photosensitive formulation and fine negative images have also been developed successfully. After cure, these cured resins exhibited the excellent combined chemical, electrical, and dielectric properties, and moisture resistance, which would make them good candidates for protecting or insulating materials for microelectronic assembly and other high-tech fields.

    30. Control of thermoresponsive property of urea end-functionalized poly(N-isopropylacrylamide) based on the hydrogen bond-assisted self-assembly in water (pages 6259–6268)

      Keita Fuchise, Ryohei Kakuchi, Sung-Tso Lin, Ryosuke Sakai, Shin-Ichiro Sato, Toshifumi Satoh, Wen-Chang Chen and Toyoji Kakuchi

      Version of Record online: 8 OCT 2009 | DOI: 10.1002/pola.23669

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      The precise synthesis and variation in the thermoresponsive property based on the supramolecular assembly of a novel urea end-functionalized poly(N-isopropylacrylamide) (PNIPAM) were studied. A series of PNIPAMs with different diphenylurea groups at the chain end were synthesized by using a combination of the atom transfer radical polymerization and the copper(I)-catalyzed azide-alkyne cycloaddition. The hydrogen-bonding property of the chain end urea group was concluded to be involved in the aggregation of the PNIPAM in water, leading to the variation in its cloud point. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    31. Synthesis of novel fluorinated hyperbranched polyimides with excellent optical properties (pages 6269–6279)

      Yu Liu, Yunhe Zhang, Shaowei Guan, Haibo Zhang, Xigui Yue and Zhenhua Jiang

      Version of Record online: 8 OCT 2009 | DOI: 10.1002/pola.23670

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      Novel anhydride-terminated fluorinated hyperbranched polyimides (FHBPIs) were successfully prepared. FHBPIs show increased mechanical properties with the linear length of dianhydride monomer. Their films also present a minimum birefringence value as low as 0.0025 at 650 nm and have low optical absorption in the optical communication wavelength. Rib-type optical waveguide device fabricated by FHBPI-4d demonstrated an obvious near-field mode pattern of the waveguide, indicating its potential use in optical waveguide devices.

    32. You have free access to this content
      A new donor–acceptor double-cable carbazole polymer with perylene bisimide pendant group: Synthesis, electrochemical, and photovoltaic properties (pages 6280–6291)

      Sermet Koyuncu, Ceylan Zafer, Fatma Baycan Koyuncu, Banu Aydin, Mustafa Can, Emre Sefer, Eyup Ozdemir and Siddik Icli

      Version of Record online: 12 OCT 2009 | DOI: 10.1002/pola.23671

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      We report here electrochemical synthesis of novel soluble donor–acceptor polymer with suitably functionalized perylenetetra-carboxylic dimide (PDI) dye derivative covalently linked to carbazole moiety (Cbz-PDI) on the optical transparent ITO/glass surface. Efficient intramolecular electron transfer from Cbz-donor to PDI-acceptor leads to remarkable fluorescence quenching of the perylene core. The photovoltaic performance of the D–A double-cable polymer is checked and about 0.1% electrical conversion efficiency is obtained under simulated AM 1.5 solar light with 100 mW/cm2 radiation power. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    33. Self-assembly of well-defined amphiphilic polymeric miktoarm stars, dendrons, and dendrimers in water: The effect of architecture (pages 6292–6303)

      Daria E. Lonsdale, Michael R. Whittaker and Michael J. Monteiro

      Version of Record online: 12 OCT 2009 | DOI: 10.1002/pola.23672

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      Five polymeric architectures with a systematic increase in architectural complexity were synthesized by ‘click’ reactions from a toolbox of functional linear polymers and small molecule linkers. The amphiphilic architectures ranged from a simple 3-miktoarm star block copolymer to the more complex 3rd generation dendrimer-like block copolymer, consisting of polystyrene (PSTY) and polyacrylic acid (PAA). Micellization of these architectures in water at a pH of 7 under identical ionic strength gave spherical micelles ranging in size from 9 to 30 nm. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    34. Synthesis of miktoarm star amphiphilic block copolymers via combination of NMRP and ATRP and investigation on self-assembly behaviors (pages 6304–6315)

      Weidong Zhang, Wei Zhang, Nianchen Zhou, Jian Zhu, Zhenping Cheng and Xiulin Zhu

      Version of Record online: 12 OCT 2009 | DOI: 10.1002/pola.23673

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      In this article, we have successfully obtained micrometer rod-shaped nanorods through self-assembly of well-defined miktoarm star amphiphilic copolymers PS(PNIPAAM-b-P4VP)2 prepared by a combination of atom transfer radical polymerization (ATRP) and nitroxide-mediated radical polymerization (NMRP). The pH value of solution had a significant effect on the morphologies of the micelles self-assembled from the PS(PNIPAAM)2 and PS(PNIPAAM-b-P4VP)2.

    35. Single electron transfer-living radical polymerization of methyl methacrylate in fluoroalcohol: Dual control over molecular weight and tacticity (pages 6316–6327)

      Wenxiang Wang, Zhengbiao Zhang, Jian Zhu, Nianchen Zhou and Xiulin Zhu

      Version of Record online: 12 OCT 2009 | DOI: 10.1002/pola.23674

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      1,1,1,3,3,3-Hexafluoro-2-propanol (HFIP) was used as the solvent in SET-LRP of MMA, with EBiB and Cu(0)/PMDETA as the respective initiator and catalyst system. The results confirmed that HFIP facilitated the polymerization with dual control over the molecular weight and tacticity of PMMA. Higher concentration of HFIP and lower reaction temperature produced higher syndiotactic ratio. This work demonstrated the good effects of fluoroalcoshol solvent on the SET-LRP, as well as the successful extension of SET-LRP to simultaneous control of the molecular weight and stereochemistry.

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      Well-defined star-shaped poly(p-benzamide) via chain-growth condensation polymerization: Use of tetra-functional porphyrin initiator to optimize star polymer formation (pages 6328–6332)

      Kazuo Yoshino, Akihiro Yokoyama and Tsutomu Yokozawa

      Version of Record online: 12 OCT 2009 | DOI: 10.1002/pola.23686

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      To optimize synthesis of well-defined tetra-armed star-shaped poly(N-octyl-p-benzamide)s with low polydispersity, polymerization of 4-(octylamino)benzoic acid ester (1) was carried out with porphyrin-cored tetra-functional initiator 3, which allowed discrimination of star polymer from concomitantly formed linear polymer by means of GPC with UV detection. Polymerization of methyl ester monomer 1b with lithium 1,1,1,3,3,3-hexamethyldisilazide (LiHMDS) at 10 °C gave the objective star-shaped polymer 4b with controlled molecular weight and narrow molecular weight distribution.

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