Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 48 Issue 16

15 August 2010

Volume 48, Issue 16

Pages 3501–3708

  1. Articles

    1. Top of page
    2. Articles
    3. Rapid Communications
    1. Precision synthesis and characterization of thymine-functionalized polyisobutylene (pages 3501–3506)

      Mustafa Y. Sen, Judit E. Puskas, David E. Dabney, Chrys Wesdemiotis and Christelle Absalon

      Article first published online: 8 JUL 2010 | DOI: 10.1002/pola.24058

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      A new two-step synthesis of polyisobutylene (PIB) with precisely one thymine functionality per chain (PIB-T) is reported. The primary hydroxyl-functionalized PIB (PIB-OH) precursor was prepared by direct functionalization via living carbocationic polymerization of isobutylene initiated by the α-methylstyrene epoxide/TiCl4 system. MALDI-time-of-flight (ToF) mass spectrum of a low molecular weight PIB-OH precursor demonstrated the effectiveness of direct functionalization by this method. A PIB-acrylate precursor (PIB-Ac) was obtained from such a PIB-OH, and the PIB-T was subsequently prepared by Michael addition of thymine across the acrylate double bond. MALDI-ToF mass spectrometry verified the presence of precisely one thymine functionality in each polymer chain.

    2. UV-induced refractive index modulation of photoreactive polymers bearing N-acylcarbazole groups (pages 3507–3514)

      T. Griesser, A. Wolfberger, M. Edler, M. Belzik, G. Jakopic, G. Trimmel and W. Kern

      Article first published online: 8 JUL 2010 | DOI: 10.1002/pola.24081

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      This study report is based on the synthesis and characterization of photoreactive polymers bearing N-acylcarbazole groups. While poly(1-(2-vinyl-9H-carbazol-9-yl)ethanone) (poly-1) undergoes a partial photochemical Fries rearrangement, poly(2-vinyl-9H-carbazole-9-carbaldehyde) (poly-2) decarbonylates smoothly when exposed to UV irradiation. Ellipsometric measurements showed that the photo-Fries rearrangement in poly-1 causes a change in refractive index by Δn = +0.01 whereas an UV-illumination of poly-2 leads to a remarkable increase of Δn = +0.03 at 650 nm. Refractive index patterns could be easily realized using photolithographic techniques. Especially the high sensitivity and photoyield make poly-2 a promising candidate for optical applications.

    3. Dendronized copolymers functionalized with crown ethers and their reversible modification through host–guest interaction (pages 3515–3522)

      Xingquan Xiong, Yongming Chen, Shu Feng and Wei Wang

      Article first published online: 8 JUL 2010 | DOI: 10.1002/pola.24106

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      Crown ether-functionalized dendronized copolymers with an alternating structure were synthesized by free radical copolymerization. Through host-guest interaction, different organic ammonium salts could be attached onto these copolymers, yielding a series of supramolecular dendronized copolymers.

    4. Single-step process to produce functionalized multiresponsive polymeric particles (pages 3523–3533)

      Antoine Bousquet, Emmanuel Ibarboure, ValÉRie HÉRoguez, Eric Papon, Christine Labrugere and Juan Rodríguez-Hernández

      Article first published online: 8 JUL 2010 | DOI: 10.1002/pola.24112

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      Monodisperse functional multiresponsive particles were prepared by encapsulation of an amphiphilic diblock copolymer during the precipitation polymerization of polystyrene and divinylbenzene in one single step. After encapsulation of the block copolymer within the microsphere, the surface modification of the particle occurs spontaneously upon exposure to water by surface segregation of the hydrophilic PDMAEMA block. Upon dispersion of the particles in acidic media, the PDMAEMA block in its charged state is soluble and does not exhibit any change by heating. At higher pH values and temperatures above 35 °C (Low-Critical Solubility Temperature of the PDMAEMA block) the hydrophilic segment collapses.

    5. Borane chain transfer reaction in olefin polymerization using trialkylboranes as chain transfer agents (pages 3534–3541)

      Wentian Lin, Hui Niu, T. C. Mike Chung and Jin-Yong Dong

      Article first published online: 8 JUL 2010 | DOI: 10.1002/pola.24125

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      This article discusses a new borane chain transfer reaction in olefin polymerization that employs trialkylboranes [triethylborane (TEB) and methyl-B-9-borabicyclononane (Me-B-9-BBN)] as chain transfer agent and thus can be realized in conventional single site polymerization processes under mild conditions. These trialkylboranes as chain transfer agent perform no less than those B[BOND]H-bearing borane derivatives, and they are additionally advantaged by a much milder reaction condition, which further boosts their applicability in the preparation of borane-terminated polyolefins.

    6. Synthesis of polyethylene and polypropylene containing fluorene units in the side chain (pages 3542–3552)

      Naofumi Naga, Hiroki Sakai, Chiharu Usui and Haruhiko Tomoda

      Article first published online: 8 JUL 2010 | DOI: 10.1002/pola.24131

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      Copolymerizations of ethylene or propylene and allyl monomers containing 9-fluorenyl group, diallyl-di-9-fluorenylsilane (DAFS), 9,9-diallylfluorene (DAF), and 9-allylfluorene (AF) were investigated with various zirconocene catalysts using methylaluminoxane as a cocatalyst. DAFS was mainly incorporated into the polymer chain via cyclization insertion, whereas, DAF was copolymerized via both 1,2- and cyclization insertions. Copolymerization with AF yielded low-molecular weight copolymer because of frequent chain transfer reaction. Optical properties of the propylene-based-copolymers were investigated by UV-vis and photoluminescence spectroscopy, and absorption and emission derived from fluorenyl groups were detected in the copolymers.

    7. Complex, degradable polyester materials via ketoxime ether-based functionalization: Amphiphilic, multifunctional graft copolymers and their resulting solution-state aggregates (pages 3553–3563)

      Rhiannon K. Iha, Brooke A. van Horn and Karen L. Wooley

      Article first published online: 8 JUL 2010 | DOI: 10.1002/pola.24132

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      Functional, degradable, amphiphilic graft copolymers of poly(ε-caprolactone)-graft-poly(ethylene oxide), PCL-g-PEO, were synthesized via a grafting onto strategy using ketones presented along the backbone of the statistical copolymer poly(ε-caprolactone)-co-(2-oxepane-1,5-dione), P(CL-co-OPD). The resulting block graft copolymers displayed unique thermal behavior and were found to undergo self-assembly in aqueous solution producing either spherical or rod-like micelles.

    8. Magnesium complexes incorporated by sulfonate phenoxide ligands as efficient catalysts for ring-opening polymerization of ε-caprolactone and trimethylene carbonate (pages 3564–3572)

      Po-Sheng Chen, Yi-Chang Liu, Chia-Her Lin and Bao-Tsan Ko

      Article first published online: 8 JUL 2010 | DOI: 10.1002/pola.24133

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      The ring-opening polymerization of ε-caprolactone (ε-CL) and trimethylene carbonate (TMC) catalyzed by efficient catalysts 1 and 2 in the presence of alcohol has been investigated. These catalytic systems have demonstrated great activity and well molecular weight control.

    9. Preparation of thermoresponsive polymers bearing amino acid diamide derivatives via RAFT polymerization (pages 3573–3586)

      Zhilei Liu, Jiwen Hu, Jianping Sun, Guping He, Yinghui Li and Ganwei Zhang

      Article first published online: 8 JUL 2010 | DOI: 10.1002/pola.24137

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      This article describes reversible addition fragmentation chain transfer polymerization (RAFT) polymerization of amino acid diamide monomer, N-acryloyl-L-valine N'-methylamide), using alkynyl-functionalized 2–dodecylsulfanylthiocarbonylsulfanyl-2-methyl-propionic acid propargyl alcohol ester as chain transfer agent and 2,2'-azobis(isobutyronitrile) as initiator. The thermoresponsive properties of the prepared polymers with different molecular weight in aqueous solution were evaluated.

    10. Synthesis and characterization of epoxy functionalized cooligomers based on chlorotrifluoroethylene and allyl glycidyl ether (pages 3587–3595)

      K. S. Santhosh Kumar and Bruno Ameduri

      Article first published online: 8 JUL 2010 | DOI: 10.1002/pola.24138

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      Functionalized fluorocooligomers based on chlorotrifluoroethylene (CTFE) and allyl glycidyl ether (AGE) were synthesized under radical copolymerization. The kinetics of radical copolymerization led to the assessment of the reactivity ratio as rCTFE = 0.20 ± 0.02 and rAGE = 0.15 ± 0.04 at 74 °C and the distribution of monomers in the cooligomers showed a tendency to alternance. The thermal stabilities of the cooligomers displayed T5% values over 225 °C under air.

    11. Facile synthesis of polyaniline hemispheres in diethyl ether/ice mixture solvent and growth mechanism study (pages 3596–3603)

      Hui-yan Ma, Yun-wu Li, Fei Cao, Yu Gao, Jian Gong and Yu-lin Deng

      Article first published online: 8 JUL 2010 | DOI: 10.1002/pola.24140

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      A facile way, an improved ice-templating method, has been developed to prepare polyaniline hemispheres with pure morphology in bulk quantity, which extends the field of functional materials with complex container structure and offers a new route to synthesis of hemispherical container structure of conducting polymers.

    12. Reducibly degradable hydrogels of PNIPAM and PDMAEMA: Synthesis, stimulus-response and drug release (pages 3604–3612)

      Bo-yu Zhang, Wei-Dong He, Li-ying Li, Xiao-li Sun, Wen-tao Li and Ke-ren Zhang

      Article first published online: 8 JUL 2010 | DOI: 10.1002/pola.24141

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      Reducibly degradable hydrogels of PNIPAM and PDMAEMA were synthesized by the combination of RAFT polymerization and click chemistry. These hydrogels exhibited temperature or pH stimulus-responsive behavior with rapid response, high swelling ratio and reproducible swelling/shrinkage cycles, and could be in drug delivery.

    13. Synthesis of water-soluble perylenediimide-functionalized polymer through esterification with poly(vinyl alcohol) (pages 3613–3622)

      Horacio J. Salavagione, Gerardo Martínez, Rafael Gómez and José L. Segura

      Article first published online: 8 JUL 2010 | DOI: 10.1002/pola.24142

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      The esterification of a perylenediimide with poly(vinyl alcohol) gives a polymeric product soluble in water and DMSO. The perylenediimide-modified polymer showed better thermal properties and retained the photophysical properties of the modifying group.

    14. Well-controlled amphiphilic block glycopolymers and their molecular recognition with lectins (pages 3623–3631)

      Orietta León, Vanesa Bordegé, Alexandra Muñoz-Bonilla, Manuel Sánchez-Chaves and Marta Fernández-García

      Article first published online: 8 JUL 2010 | DOI: 10.1002/pola.24143

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      Well-controlled homoglycopolymers based on unprotected glycomonomer, 2-{[(D-glucosamin-2N-yl)carbonyl]oxy}ethyl methacrylate (HEMAGl) as well as their amphiphilic di and triblock copolymers with n-butyl acrylate are obtained by atom transfer radical polymerization. The strong aggregation of these glycopolymers in distilled water is partially disturbed by the addition of NaCl. The molecular weight and the copolymer composition of block glycopolymers affect the interaction with Concanavalin A lectin.

    15. Ring opening polymerization of lactide promoted by alcoholyzed heteroscorpionate aluminum complexes (pages 3632–3639)

      Antonella Silvestri, Fabia Grisi and Stefano Milione

      Article first published online: 8 JUL 2010 | DOI: 10.1002/pola.24145

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      The alcoholysis of the heteroscorpionate methyl aluminum complex (bpzmp)AlMe2 and the application of the corresponding alkoxide derivatives in the ring opening polymerization of lactides is described. The isopropoxy derivative was proved to be an effective preinitiator for ring opening polymerization of lactide. Under the investigated polymerization conditions, a good molar-mass control was shown. This study has uncovered the strong and sometime unexpected influence that alcoholysis processes have on the activation of the aluminum based precatalysts in the ring opening polymerization of the cyclic esters.

    16. Sulfonated polybenzimidazoles: Proton conduction and acid–base crosslinking (pages 3640–3650)

      Owen D. Thomas, Timothy J. Peckham, Uma Thanganathan, Yunsong Yang and Steven Holdcroft

      Article first published online: 8 JUL 2010 | DOI: 10.1002/pola.24147

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      Blends made of sulfonated poly(benzimidazole) (SuPBI) and high IEC sulfonated poly(ether ether ketone) have been made and the properties of these membranes have been investigated. Comparisons made between sulfonated and nonsulfonated poly(benzimidazole) show an increase in proton conductivity in blends using SuPBI at elevated temperatures (90 °C).

    17. Specific recognition of syndiotactic poly(methacrylic acid) in porous isotactic poly(methyl methacrylate) thin films based on the effects of stereoregularity, temperature, and solvent (pages 3651–3657)

      Daisuke Kamei, Hiroharu Ajiro and Mitsuru Akashi

      Article first published online: 8 JUL 2010 | DOI: 10.1002/pola.24148

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      The effects of stereoregularity, temperature, and solvent on the incorporation behavior of syndiotactic (st)-poly(methacrylic acid) (PMAA) in porous isotactic (it)-PMMA were analyzed by QCM and IR spectroscopy. The incorporation depended on stereoregularity of st-PMAA (rr = 94, 73, and 62, respectively), and was promoted with increasing temperature (from 25 to 40 °C). st-PMAA was only incorporated when a specific solvent, acetonitrile/water or ethanol/water, was selected from complexing solvents.

    18. 9,9′-spirobifluorene-containing polycarbonates: Transparent polymers with high refractive index and low birefringence (pages 3658–3667)

      Ryota Seto, Takashi Sato, Takahiro Kojima, Katsumoto Hosokawa, Yasuhito Koyama, Gen-Ichi Konishi and Toshikazu Takata

      Article first published online: 8 JUL 2010 | DOI: 10.1002/pola.24150

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      9,9′-Spirobifluorene-containing polycarbonates (PC 4) were synthesized by the polycondensation of 2,2′-bisalcoholic monomers 2 and triphosgene or diphenyl carbonate. The refractive index of PC 4 was higher than that of 9,9-diarylfluorene-containing polymer, whereas PC 4 hardly showed birefringence due to the perfectly C2-symmetric structure of 2.

    19. Synthesis, characterization, electrochromic properties, and electrochromic device application of a novel star polymer consisting of thiophene end-capped poly(ε-caprolactone) arms emanating from a hexafunctional cyclotriphosphazene core (pages 3668–3682)

      Mesut Gorur, Faruk Yilmaz, Adem Kilic, Ali Demirci, Yusuf Ozdemir, Arif Kosemen and Sait Eren San

      Article first published online: 8 JUL 2010 | DOI: 10.1002/pola.24151

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      A star polymer with phosphazene core and thiophene end-capped six poly(ε-caprolactone) arms were synthesized in a four-step sequence via core first approach. Ring-opening polymerization and “click” chemistry techniques were employed in the first and final steps, respectively. Polymerizable thiophene end groups of the star polymer were employed in electrochemical copolymerization with thiophene and pyrrole. The copolymer obtained from the electropolymerization reaction between the star polymer and thiophene was also used in electrochromic device application.

    20. Sequential conversion of orthogonally functionalized diblock copolymers based on pentafluorophenyl esters (pages 3683–3692)

      Katja Nilles and Patrick Theato

      Article first published online: 8 JUL 2010 | DOI: 10.1002/pola.24152

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      Orthogonally functionalized block copolymers with one specific reactive group, namely active pentafluorophenyl esters, and their sequential conversion with different amines.

    21. Synthesis of highly luminescent organoboron polymers connected by bifunctional 8-aminoquinolate linkers (pages 3693–3701)

      Yuichiro Tokoro, Atsushi Nagai and Yoshiki Chujo

      Article first published online: 8 JUL 2010 | DOI: 10.1002/pola.24153

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      New organoboron aminoquinolate-based polymers linked by π-conjugated bridge were prepared by Sonogashira–Hagihara coupling. The absorption and emission bands in the region above 400 nm predominantly depended on the structure composed of two quinoline rings and diethynylbenzene. The polymers with biphenyl group exhibited the high fluorescence absolute quamtum yield, whereas the polymer with the bithiophene moiety and the perfluoroalkyl chain showed almost no emission. This result and the density-functional theory calculations on the molecular model systems of the polymers suggested that the electron transfer easily occurs from bithiophene moiety to the π-extended quinoline moiety in transition state.

  2. Rapid Communications

    1. Top of page
    2. Articles
    3. Rapid Communications
    1. You have free access to this content
      A stepping stone to stereospecific living cationic polymerization: Cationic polymerization of vinyl ethers using iron(II) sulfate (pages 3702–3708)

      Arihiro Kanazawa, Shokyoku Kanaoka and Sadahito Aoshima

      Article first published online: 8 JUL 2010 | DOI: 10.1002/pola.24144

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      Stereospecific cationic polymerization of vinyl ethers (VEs) was investigated using iron(II) sulfate as a catalyst under various conditions, focusing on the improvement of stereoregulation ability and the dual control of stereoregularity and molecular weight. In conjunction with tBuOH, polymerization of isobutyl VE proceeded in relatively controlled fashion, indicating the production of long-lived species. In addition, the molecular weight of the stereoregulated portion, obtained as a methyl ethyl ketone-insoluble fraction, increased with the procession of the reaction. The results showed a clue to stereospecific living cationic polymerization.

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