Journal of Polymer Science Part A: Polymer Chemistry

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

15 September 2010

Volume 48, Issue 18

Pages 3913–4139

  1. Articles

    1. Top of page
    2. Articles
    1. Experimental and theoretical investigation of a new rapid switching near-infrared electrochromic conjugated polymer (pages 3913–3923)

      Han-Yu Wu, Kun-Li Wang, Jyh-Chiang Jiang, Der-Jang Liaw, Kueir-Rarn Lee, Juin-Yih Lai and Ci-Liang Chen

      Version of Record online: 5 AUG 2010 | DOI: 10.1002/pola.24104

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      A novel rapid switching near-IR electrochromic conjugated polymer containing di-triarylamine group was synthesized and investigated. The polymer showed excellent continuous cyclic stability of electrochromic characteristic with rapid color switching time 2.58 s and bleaching time 1.76 s. A redox mechanism of the material was suggested and studied by theoretical calculation based on molecular orbital theory on the basis of the cyclic voltammetry and electrochromic experimental results.

    2. Characterization of poly(methyl methacrylate) nanoparticles prepared by nanoprecipitation using analytical ultracentrifugation, dynamic light scattering, and scanning electron microscopy (pages 3924–3931)

      Igor Perevyazko, Antje Vollrath, Stephanie Hornig, Georges M. Pavlov and Ulrich S. Schubert

      Version of Record online: 5 AUG 2010 | DOI: 10.1002/pola.24157

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      Nanoparticles of synthetic hydrophobic polymers [poly(methyl methacrylates)] were obtained by different nanoprecipitation methods in the scale of diameter: 6 ≤ d, nm ≤ 600. The particles were characterized by SEM, DLS, and velocity sedimentation methods.

    3. Synthesis of biocompatible and thermally sensitive poly(N-vinylcaprolactam) nanogels via inverse miniemulsion polymerization: Effect of the surfactant concentration (pages 3932–3941)

      Simone F. Medeiros, Amilton M. Santos, Hatem Fessi and Abdelhamid Elaissari

      Version of Record online: 5 AUG 2010 | DOI: 10.1002/pola.24165

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      Thermally sensitive poly(N-vinylcaprolactam) nanogels have been prepared via inverse miniemulsion polymerization. The effect of an oil-soluble surfactant sorbitan monooleate (Span 80) on the nanogels diameter, polymerization rate, and thermoproperties was studied. At Span 80 concentrations between 3% and 8% with respect to the continuous phase, all the nanogels were stable. With the analyses of the average hydrodynamic diameter, the prepared particles exhibit thermoresponsive property and the TEM analysis confirmed the spherical morphology of the formed particles. The results obtained are especially interesting for the study of this system as encapsulation agents for inorganic nanoparticles for in vivo applications.

    4. Synthesis and characterization of poly(1,4-bis((E)-2-(3-dodecylthiophen-2-yl)vinyl)benzene) derivatives (pages 3942–3949)

      Min-Jung Lee, Moon Seong Kang, Min-Ki Shin, Jong-Won Park, Dae Sung Chung, Chan Eun Park, Soon-Ki Kwon and Yun-Hi Kim

      Version of Record online: 5 AUG 2010 | DOI: 10.1002/pola.24174

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      New amorphous semiconducting copolymers, poly(9,9-dialkylfluorene)-alt-(3-dodecylthienyl-divinylbenzene-3-dodecylthienyl) derivatives (PEFTVB and POFTVB), were designed, synthesized, and characterized. The solution-processed thin-film transistors showed the carrier mobility of 2 × 10−4 cm2 V−1 s−1 for PEFTVB-based devices and 2× 10−5 cm2 V−1 s−1 for POFTVB-based devices.

    5. Free radical initiated low temperature crosslinking of phenylethynyl (PE) end-capped oligomides (pages 3950–3963)

      Chenliang Gong, Qiang Luo, Yanfeng Li, Marcus Giotto, Ned E. Cipollini, Zhiwei Yang, R. A. Weiss and Daniel A. Scola

      Version of Record online: 5 AUG 2010 | DOI: 10.1002/pola.24178

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      Schematic of crosslinked polyimide structure plasticized with degradative polymerized DM-PEG-250 or PEG-400.

    6. Radical copolymerization of vinylidene fluoride with 1-bromo-2,2-difluoroethylene (pages 3964–3976)

      G. K. Kostov, L. Sauguet, B. Ameduri, H. Kaspar, T. Zipplies and K. Hintzer

      Version of Record online: 5 AUG 2010 | DOI: 10.1002/pola.24179

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      The radical copolymerization of vinylidene fluoride (VDF) with 1-bromo-2,2-difluoroethylene (BDFE) is presented as follows: The reactivity ratios ri of both comonomers (rVDF = 1.20 ± 0.50 and rBDFE = 0.41 ± 0.16 at 75 °C) were assessed and the thermal properties were investigated.

    7. A reduction sensitive cascade biodegradable linear polymer (pages 3977–3985)

      Matthew A. Dewit, Annelise Beaton and Elizabeth R. Gillies

      Version of Record online: 5 AUG 2010 | DOI: 10.1002/pola.24180

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      Cascade degradable linear polymers comprise a backbone that is stable in the presence of an end cap, but upon removal of the end cap a cascade of intramolecular reactions is initiated that leads to depolymerization. A new polymer backbone based on N,N′-dimethylethylenediamine and 2-mercaptoethanol linked by carbamates and thiocarbamates was developed. A disulfide end cap was incorporated such that its cleavage under reducing conditions revealed the thiol of 2-mercaptoethanol, leading to alternating cyclizations of the 2-mercaptoethanol and N,N′-dimethylethylenediamine moieties to provide 1,3-oxathiolan-2-one and N,N′-dimethylimidazolidinone respectively.

    8. Amino acid-functionalized ethyl cellulose: Synthesis, characterization, and gas permeation properties (pages 3986–3993)

      Yoshitaka Ikeuchi, Fareha Zafar Khan, Naoya Onishi, Masashi Shiotsuki, Toshio Masuda, Yoshiyuki Nishio and Fumio Sanda

      Version of Record online: 5 AUG 2010 | DOI: 10.1002/pola.24181

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      Ethyl cellulose (EC), an organosoluble cellulosic of remarkable commercial and pharmaceutical significance, has been functionalized with amino acids, one of the basic building blocks of nature. The amino acid esters of EC were characterized by 1H NMR spectroscopy. The substitution of hydroxy protons of EC by bulky amino acid functionalities accompanied a decrease in glass transition temperature without any detriment to organosolubility. Free-standing membranes could be fabricated, and the incorporation of polar aminoalkanoyl moieties imparted enhanced permselectivity for CO2/N2 and CO2/CH4 gas pairs.

    9. s-Triazine-based hyperbranched polyethers: Synthesis, characterization, and properties (pages 3994–4004)

      Niranjan Karak, Buddhadeb Roy and Brigitte Voit

      Version of Record online: 5 AUG 2010 | DOI: 10.1002/pola.24183

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      Hyperbranched flexible polyethers with s-triazine unit in the main chain have been synthesized and characterized, and thermal properties were evaluated. An analogous linear polyether was also prepared and results were compared. The polymerization reaction parameters were optimized to obtain optimum yields, viscosity, and hydroxyl values.

    10. Facile synthesis of N-vinylimidazole-based hydrogels via frontal polymerization and investigation of their performance on adsorption of copper ions (pages 4005–4012)

      Jun Tu, Jin Zhou, Cai-Feng Wang, Qiang Zhang and Su Chen

      Version of Record online: 5 AUG 2010 | DOI: 10.1002/pola.24184

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      This article reports a new strategy to quickly synthesize pH sensitive poly(VI-co-HEA) hydrogels by frontal polymerization. The as-prepared hydrogels have good pH sensitivity and can be applied to remove heavy metals.

    11. Hyperbranched-upon-dendritic macromolecules as unimolecular hosts for controlled release (pages 4013–4019)

      Changlei Xia, Xiangyu Ding, Yan Sun, Hewen Liu and Yuesheng Li

      Version of Record online: 5 AUG 2010 | DOI: 10.1002/pola.24185

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      The hyperbranched-upon-dendritic polymers could be used as unimolecular nanocarriers with controllable encapsulation dosage for controlled release.

    12. Preparation, characterization, and properties of fluorene-containing benzoxazine and its corresponding cross-linked polymer (pages 4020–4026)

      Ying-Ling Liu, Che-Yuan Chang, Chih-Yuan Hsu, Min-Chi Tseng and Ching-I Chou

      Version of Record online: 5 AUG 2010 | DOI: 10.1002/pola.24187

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      This work reports the preparation of a di-functional and fluorene-containing benzoxazine compound and the corresponding cross-linked polybenzoxazine resin as well as study the photoluminescent behavior and thermal properties of the materials.

    13. Synthesis of polyoxazolines using glycerol carbonate derivative and end chains functionalization via carbonate and isocyanate routes (pages 4027–4035)

      Chloe Giardi, Vincent Lapinte, Françoise Nielloud, Jean-Marie Devoisselle and Jean-Jacques Robin

      Version of Record online: 5 AUG 2010 | DOI: 10.1002/pola.24188

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      The synthesis of polyoxazoline has been achieved via cationic ring-opening polymerization of 2-methyl-2-oxazoline using glycerol carbonate derivative as bio-based initiator. The article focuses on end group modifications using isocyanate and carbonate routes.

    14. Synthesis of copolyimides based on room temperature ionic liquid diamines (pages 4036–4046)

      Pei Li, Qichao Zhao, Jared L. Anderson, Sasidhar Varanasi and Maria R. Coleman

      Version of Record online: 5 AUG 2010 | DOI: 10.1002/pola.24189

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      Two diamino room temperature ionic liquids (RTILs) were synthesized. The RTILs were copolymerized within 6FDA-MDA backbones and formed (6FDA-RTIL)x-(6FDA-MDA)n-x block copolyimides to modify gas transport properties. The 6FDA-RTIL blocks contained more flexible alkyl groups which resulted in denser packing of the block copolyimides. Therefore, the RTIL based block copolyimides exhibited a decrease in gas permeability and an increase in permeability selectivity relative to the pure 6FDA-MDA.

    15. Temperature-sensitive hyperbranched poly(glycidol)s with oligo(ethylene glycol) monoethers (pages 4047–4054)

      Chie Kojima, Kohei Yoshimura, Atsushi Harada, Yuichi Sakanishi and Kenji Kono

      Version of Record online: 5 AUG 2010 | DOI: 10.1002/pola.24190

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      Biocompatible and temperature-dependent hyperbranched poly(glycidol)s (HPGs) were synthesized and characterized. HPGs were succinylated, and then modified with the oligo(ethylene glycol) monoethers (OEG). These polymers exhibited phase transitions at a specific temperature (the cloud point), depending on the composition of OEG. By tuning the composition of OEG in the polymer, thermosensitive polymers with cloud point near body temperature were produced. Because they exhibited no cytotoxicity, these temperature-sensitive polymers are useful for biomedical applications.

    16. Doubly photoresponsive and water-soluble block copolymers: Synthesis and thermosensitivity (pages 4055–4066)

      Yi Zhao, Luc Tremblay and Yue Zhao

      Version of Record online: 5 AUG 2010 | DOI: 10.1002/pola.24191

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      A new type of photoresponsive block copolymers (BCPs) was synthesized and studied. They were designed to comprise two water-soluble polymers containing two different photoisomerizable moieties such as azobenzene and spiropyran. Their thermal phase transition behaviors in aqueous solution before and after simultaneous photoreactions on the two blocks were investigated in comparison with their constituting blocks. It was found that such BCPs could display a single LCST determined by competing photoinduced effects on the two blocks, and that optically controlling the relative photoisomerization degrees of trans azobenzene-to-cis azobenzene and spiropyran-to-merocyanine could be used to tune the LCST.

    17. A hyperbranched, rotaxane-type mechanically interlocked polymer (pages 4067–4073)

      Shijun Li, Bo Zheng, Jianzhuang Chen, Shengyi Dong, Zhi Ma, Feihe Huang and Harry W. Gibson

      Version of Record online: 5 AUG 2010 | DOI: 10.1002/pola.24192

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      Based on the dibenzo-24-crown-8/1,2-bis(pyridinium)ethane recognition motif, a hyperbranched mechanically interlocked polymer was prepared by polyesterification of an easily available dynamic trifunctional AB2 pseudorotaxane monomer. It was characterized by various techniques including 1H NMR, COSY, NOESY, GPC, viscosity, TGA, dynamic laser light scattering, AFM, and SEM. Its GPC Mn was determined to be 191 kDa with polydispersity 1.7 and its hydrodynamic diameter in a dilute solution in acetone was about 70 nm. This measured Mn value corresponds to about 93 repeating units. The study reported here presents not only a new polymer topology but also a novel and convenient way to prepare mechanically interlocked polymers.

    18. Mesoglobules of random copolyethers as templates for nanoparticles (pages 4074–4083)

      Barbara Trzebicka, Paweł Weda, Alicja Utrata-Wesołek, Andrzej Dworak and Christo Tsvetanov

      Version of Record online: 5 AUG 2010 | DOI: 10.1002/pola.24193

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      Stimuli responding particles are useful and frequently studied objects, also for controlled immobilization and delivery of active species.

      The article describes a new type of thermosensitive nanoparticles. It is shown that if proper conditions are applied (rate of temperature changes, concentration of polymer, and addition of surfactant), the novel thermosensitive polymer, poly(glycidol-co-ethyl glicydyl carbamate), forms the cores of controlled size from 150 to 400 nanometer diameter.

      These cores nucleate the polymerization of NIPAM. As a result, doubly thermosensitive core-shell nanoparticles are obtained.

    19. The synthesis of water-soluble PHEMA via ARGET ATRP in protic media (pages 4084–4092)

      Stefan M. Paterson, David H. Brown, Traian V. Chirila, Imelda Keen, Andrew K. Whittaker and Murray V. Baker

      Version of Record online: 5 AUG 2010 | DOI: 10.1002/pola.24194

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      2-Hydroxyethyl methacrylate has been polymerized in methanol using activators regenerated by electron transfer (ARGET) atom transfer radical polymerization (ATRP), to produce water-soluble poly(2-hydroxyethyl methacrylate) (PHEMA). The various parameters that determine control of the living polymerization have been explored, including, the copper-to-ligand ratios, the concentration of the reducing agent (ascorbic acid or hydrazine) and the initiator to monomer ratios. PHEMA was also synthesized by ARGET ATRP in the nondegassed prepolymer solutions.

    20. Kinetics of bulk azide/alkyne “click” polymerization (pages 4093–4102)

      Xia Sheng, Timothy C. Mauldin and Michael R. Kessler

      Version of Record online: 5 AUG 2010 | DOI: 10.1002/pola.24196

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      With a goal of developing monomer systems for low-cost self-healing applications, two alkyne/azide systems (bisphenol E diyne/bisphenol A bisazide and tetraethylene glycol diyne/bisphenol A bisazide) were prepared and evaluated. The “click” bulk polymerization kinetics for these alkyne/azide systems, and the effect of catalyst concentration, were investigated with DSC dynamic scans at different heating rates. The kinetic model developed suggests that the bulk “click” polymerization follows nth order reaction kinetics with a reaction order of about 1.2 for all samples except B/B-3, which follows autocatalytic reaction kinetics and has a total reaction order (n + m) of1.9.

    21. Single-molecule imaging of photodegradation reaction in a chiral helical π-conjugated polymer chain (pages 4103–4107)

      Ken-ichi Shinohara, Noriyuki Kodera and Takashi Oohashi

      Version of Record online: 5 AUG 2010 | DOI: 10.1002/pola.24201

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      In this study, we succeeded for the first time in the direct measurement of when, where, and how the chemical reaction of a polymer chain on a nanometer scale proceeds. That is, single-molecule imaging of the photodegradation reaction of a chiral helical π-conjugated polymer following laser irradiation of 405 nm was conducted. Analysis of the chemical kinetics showed that the photodegradation of the single polymer chain proceeded stepwise as a quantum phenomenon. When the motility of the chain-end increased, reactivity of the photodegradation increased. It was also discovered that the photodegradation of the polymer chain proceeded continuously in one direction, like the “domino effect.”

    22. Amphiphilic silicones prepared from branched PEO-silanes with siloxane tethers (pages 4108–4119)

      Ranjini Murthy, Brennan M. Bailey, Celimar Valentin-Rodriguez, Albena Ivanisevic and Melissa A. Grunlan

      Version of Record online: 5 AUG 2010 | DOI: 10.1002/pola.24203

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      Amphiphilic silicones were prepared by the covalent incorporation of branched polyethylene oxide (PEO) via a siloxane tether. Branched PEO-silanes with varying siloxane tether lengths and PEO molecular weight were crosslinked with α,ω-bis(Si[BOND]OH)PDMS. As siloxane tether length was increased, film surface hydrophilicity increased, particularly after exposure to an aqueous environment, indicating that the PEO segments buried in the bulk were more readily driven to the surface. As a result, adsorption of bovine serum albumin (BSA) and human fibrinogen (HF) proteins decreased with siloxane tether length, particularly after first exposing films to an aqueous environment.

    23. Lead-sensitive PNIPAM microgels modified with crown ether groups (pages 4120–4127)

      Qiaofang Luo, Ying Guan, Yongjun Zhang and Muhammad Siddiq

      Version of Record online: 5 AUG 2010 | DOI: 10.1002/pola.24205

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      Poly(N-isopropylacrylamide) microgels with pendant crown ether groups were prepared, which swell in the presence of Pb2+ as a result of the formation of host–guest complex between Pb2+ and crown ether groups.

    24. Mesophase structure of low-wetting liquid crystalline polyacrylates with new perfluoroalkyl benzoate side groups (pages 4128–4139)

      Elisa Martinelli, Francesca Paoli, Bernard Gallot and Giancarlo Galli

      Version of Record online: 5 AUG 2010 | DOI: 10.1002/pola.24207

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      New polyacrylates carrying spaced 4-perfluoroalkylpropyl benzoate units in the side groups were synthesized, and their thermal behavior, bulk microstructure, and wettability were investigated. X-ray diffraction analysis proved the formation of different smectic mesophases (SmI2, SmF2, and SmC2), with a polymorphic behavior dependent on the length of the perfluorinated chain segment. The electron density profiles along the smectic layer normal pointed to a packing of the side chains in a tilted, double layer structure. Thin polymer films exhibited low wettability. We suggest that the hydrophobicity and lipophobicity of the films are enhanced by a mesophase surface structure.

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