Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 51 Issue 22

15 November 2013

Volume 51, Issue 22

Pages i–iv, 4717–4943

  1. Cover Image

    1. Top of page
    2. Cover Image
    3. Rapid Communication
    4. Articles
    1. You have free access to this content
      Cover Image, Volume 51, Issue 22 (pages i–ii)

      Article first published online: 9 OCT 2013 | DOI: 10.1002/pola.26965

      Thumbnail image of graphical abstract

      Designing 3D hydrogels with user-defined geometries can facilitate a variety of basic research in biomaterials science and tissue engineering. In their article on page 4799, R.Liska, X.-H. Qin, and coworkers report the direct assembly of 3D hydrogel structures with free-transport properties via two-photon thiolene lithography. This study reports the first biomacromolecule with pendant, low cytotoxic vinyl ester groups and subsequent copolymerization with free cysteines donated by reduced albumin. The cover image shows a 3D hydrogel construct (480 × 580 × 75 μm3) consisting of three layers of packed cylinders with a hexagonal arrangement. This method may lead researchers to better understand how cells detect and respond to their micro-environmental signals.

    2. You have free access to this content
      Cover Image, Volume 51, Issue 22 (pages iii–iv)

      Article first published online: 9 OCT 2013 | DOI: 10.1002/pola.26966

      Thumbnail image of graphical abstract

      A generation 3.5 poly(amido amine) dendron containing a 16 n-butyl terminal group-bearing acrylamide monomer (AaUG3.5) is prepared by Kazuki Osawa, Toyoko Imae, Masaki Ujihara, Atsushi Harada, Kanako Ochi, Kazuhiko Ishihara, and Shin-ichi Yusa on page 4923. AaUG3.5 is polymerized using a poly(2-methacryloyloxyethyl phosphorylcholine) (pMPC)-based macro-chain transfer agent via reversible addition–fragmentation chain transfer radical polymerization to obtain amphiphilic diblock copolymers (pMPC-b-pAaUG3.5) with different compositions. pMPC-b-pAaUG3.5 forms vesicles or large compound micelles depending on the composition.

  2. Rapid Communication

    1. Top of page
    2. Cover Image
    3. Rapid Communication
    4. Articles
    1. The role of electron pair donors in the carbocationic copolymerization of isobutylene with alloocimene (pages 4717–4721)

      Attila L. Gergely, Ozlem Turkarslan, Judit E. Puskas and Gabor Kaszas

      Article first published online: 11 SEP 2013 | DOI: 10.1002/pola.26915

      Thumbnail image of graphical abstract

      The role of electron pair donors in the carbocationic polymerizations of isobutylene is still debated. Here, the copolymerization of isobutylene and alloocimene initiated by trimethyl pentyl chloride/TiCl4 in hexane(s)/MeCl (60/40 v/v) solvent system at −80 °C with di-tert-butylpyridine as a proton trap displays the rapid monomer consumption phenomenon in the absence of dimethyl acetamide. In contrast, the copolymerization is living in the presence of dimethyl acetamide.

  3. Articles

    1. Top of page
    2. Cover Image
    3. Rapid Communication
    4. Articles
    1. Synthesis of electroactive and biodegradable multiblock copolymers based on poly(ester amide) and aniline pentamer (pages 4722–4731)

      Li Song, Baoguo Du, Li Chen, Mingxiao Deng, Hai Sun, Xuan Pang, Peibiao Zhang and Xuesi Chen

      Article first published online: 26 AUG 2013 | DOI: 10.1002/pola.26900

      Thumbnail image of graphical abstract

      A new family of poly(ester amide)-b-aniline pentamer multiblock copolymers was synthesized via a two-stage active solution polycondensation. The copolymers inherited the biodegradability and electroactivity from poly(ester amide) (PEA) and aniline pentamer (AP) blocks, respectively. In vitro cell culture data revealed that these copolymers had a good biocompatibility and supported the proliferation of RSC96 cells.

    2. Preparation of co-polymethyl(alkoxy)siloxanes by acid-catalyzed controlled hydrolytic copolycondensation of methyl(trialkoxy)silane and tetraalkoxysilane (pages 4732–4741)

      Takahiro Gunji, Takayoshi Tozune, Hironori Kaburaki, Kouji Arimitsu and Yoshimoto Abe

      Article first published online: 26 AUG 2013 | DOI: 10.1002/pola.26904

      Thumbnail image of graphical abstract

      Polymethyl(alkoxy)siloxane copolymers are prepared by acid-catalyzed controlled hydrolytic copolycondensation of methyl(trialkoxy)silane and tetra-alkoxyysilane. The products are stable to self-condensation and soluble in common organic solvents except for hexane. These polymers form flexible and transparent free-standing films that are composed of a micro-phase separated structure. The free-standing films show better weathering stability.

    3. Synthesis and characterization of naphtho[2,1-b:3,4-b′]dithiophene-based polymers with extended π-conjugation systems for use in bulk heterojunction polymer solar cells (pages 4742–4751)

      Yu Jin Kim, Yun-Ji Lee, Jae-Wan Jang, Hyojung Cha, Yun-Hi Kim, Soon-Ki Kwon and Chan Eon Park

      Article first published online: 30 SEP 2013 | DOI: 10.1002/pola.26908

      Thumbnail image of graphical abstract

      Naphthodithiophene-based polymers, PNDT-TTT and PNDT-TET, with extended π-conjugation systems showed stronger and red-shifted absorption in comparison with PNDT-T, which resulted in high short circuit currents in the organic solar cells. The PNDT-TET- and PNDT-TTT-based devices produced better photovoltaic performances, with power conversion efficiencies of 3.5 and 3.3%, respectively, compared to the PNDT-T-based device (1.3%).

    4. Homopolycyclotrimerization of A4-type tetrayne: A new approach for the creation of a soluble hyperbranched poly(tetraphenylethene) with multifunctionalities (pages 4752–4764)

      Rongrong Hu, Jacky W. Y. Lam, Min Li, Haiqin Deng, Jie Li and Ben Zhong Tang

      Article first published online: 26 AUG 2013 | DOI: 10.1002/pola.26897

      Thumbnail image of graphical abstract

      Conjugated hyperbranched polyarylene with the aggregation-enhanced emission (AEE) feature is fabricated by homopolycyclotrimerization of tetraphenylethene-containing A4-type tetrayne. The polymer is soluble and can be processed into a microporous thin film. Its AEE effect enables the monitoring of the breath figure formation. Its high-tech applications such as fluorescent chemosensors, light-refractive and photoresist materials, and precursors to magnetic ceramics are explored.

    5. Förster resonance energy transfer in poly(methyl methacrylates) copolymers bearing donor–acceptor 1,3-thiazole dyes (pages 4765–4773)

      Christian Pietsch, Johann Schäfer, Roberto Menzel, Rainer Beckert, Jürgen Popp, Benjamin Dietzek and Ulrich S. Schubert

      Article first published online: 9 SEP 2013 | DOI: 10.1002/pola.26898

      Thumbnail image of graphical abstract

      The Förster resonance energy transfer properties in poly(methyl methacrylate) copolymers containing 2-(pyridine-2-yl) thiazole dyes were studied upon systematic variation of the donor-to-acceptor ratio. The copolymers containing these energy donor and acceptor molecules were synthesized using the reversible addition-fragmentation chain transfer (RAFT) polymerization method, whereby these donor–acceptor pairs were incorporated within one polymer chain. The Förster resonance energy transfer properties of the copolymers are characterized by a steady state and time-resolved fluorescence spectroscopy. The results indicate that the energy transfer rates and the transfer efficiencies are tunable by variation of the donor-to-acceptor ratio.

    6. Alkyne-containing phthalonitrile resins: Controlling mechanical properties by selective curing (pages 4774–4778)

      Matthew Laskoski, Dawn D. Dominguez and Teddy M. Keller

      Article first published online: 26 AUG 2013 | DOI: 10.1002/pola.26899

      Thumbnail image of graphical abstract

      A phthalonitrile monomer containing an internal alkynyl group was synthesized, characterized, and converted thermally to a thermosetting polymer. Upon curing to a thermoset, the oligomeric phthalonitrile polymer exhibited excellent thermo-oxidative stability and better mechanical properties when compared to a non-alkyne resin system.

    7. Anisotropic janus magnetic polymeric nanoparticles prepared via miniemulsion polymerization (pages 4779–4785)

      Chariya Kaewsaneha, Pramuan Tangboriboonrat, Duangporn Polpanich, Mohamed Eissa and Abdelhamid Elaissari

      Article first published online: 26 AUG 2013 | DOI: 10.1002/pola.26902

      Thumbnail image of graphical abstract

      Janus magnetic polymeric nanoparticles are prepared via a miniemulsion polymerization technique. During polymerization, phase separation between the polymer and magnetic nanoparticles occurs inside the monomer, which leads to magnetic nanoparticles accumulating on one side of the particle. The anisotropic Janus magnetic polymeric nanoparticles (250 nm) obtained can easily be separated from secondary particles by an external magnet.

    8. Polymeric microstructures and dielectric properties of polynorbornenes with 3,5-bis(trifluoromethyl)biphenyl side groups by ring-opening metathesis polymerization (pages 4786–4798)

      Zewang You, Wei Song, Sha Zhang, Ouyue Jin and Meiran Xie

      Article first published online: 26 AUG 2013 | DOI: 10.1002/pola.26901

      Thumbnail image of graphical abstract

      exo-Polynorbornenes containing bis(trifluoromethyl)biphenyl side groups were synthesized by ring-opening metathesis polymerization using different Grubbs' catalysts. exo-PTNP and exo-PTNDI formed by Ru-I contain a trans double bond bias of 67–83%, whereas the corresponding polymers by Ru-III have lower trans double bond contents of 30–50%. The dielectric constants of endo-PTNP by Ru-III, and exo-PTNDIs, as well as exo-PTNPs by Ru-I or Ru-III, are much lower (6–9) than that of highly trans isotactic endo-PTNP by Ru-I (20), likely due to their dipolement being cancelled out and their lack of tacticity.

    9. Three-dimensional microfabrication of protein hydrogels via two-photon-excited thiol-vinyl ester photopolymerization (pages 4799–4810)

      Xiao-Hua Qin, Jan Torgersen, Robert Saf, Severin Mühleder, Niklas Pucher, S. Clark Ligon, Wolfgang Holnthoner, Heinz Redl, Aleksandr Ovsianikov, Jürgen Stampfl and Robert Liska

      Article first published online: 2 SEP 2013 | DOI: 10.1002/pola.26903

      Thumbnail image of graphical abstract

      The spatiotemporal 3D printing of hydrogels with user-dictated structures is promising for current biomaterials research. However, the lack of appropriate fabrication techniques and robust polymerization approaches remain hurdles. A new cytocompatible hydrogel precursor (vinyl ester derivative of gelatin) and subsequent two-photon excited thiol-vinyl ester photopolymerization are introduced. By using robust two-photon chemistry, it is possible to simultaneously pattern two proteins into user-defined 3D structures with a high writing speed.

    10. Double metal cyanide catalyst prepared using H3Co(CN)6 for high carbonate fraction and molecular weight control in carbon dioxide/propylene oxide copolymerization (pages 4811–4818)

      Jobi Kodiyan Varghese, Dong Sik Park, Jong Yeob Jeon and Bun Yeoul Lee

      Article first published online: 26 AUG 2013 | DOI: 10.1002/pola.26905

      Thumbnail image of graphical abstract

      Simple mixing of H3Co(CN)6 and ZnCl2 resulted in precipitates of [ZnCl]+2[HCo(CN)6]2−, constituting a new type of double metal cyanide catalyst exhibiting high performance in CO2/PO copolymerization. Poly(propylene carbonate−co−propylene oxide)s were consistently obtained with high carbonate fractions (∼60 mol%) and a high selectivity (>90%).

    11. Optimal estimation of reactivity ratios for acrylamide/acrylic acid copolymerization (pages 4819–4827)

      Marzieh Riahinezhad, Niousha Kazemi, Neil McManus and Alexander Penlidis

      Article first published online: 2 SEP 2013 | DOI: 10.1002/pola.26906

      Thumbnail image of graphical abstract

      In a copolymerization system, it is imperative to determine monomer reactivity ratios for better polymer microstructure control. The reactivity ratios of the important copolymerization of acrylamide/acrylic acid, a water-soluble copolymer, exhibit considerable scatter in the literature. The reasons for inconsistency in these values and is discussed, and an appropriate general methodology is applied for the first time in order to determine reliable reactivity ratios.

    12. Living cationic polymerization of vinylnaphthalene derivatives (pages 4828–4834)

      Yu Shinke, Arihiro Kanazawa, Shokyoku Kanaoka and Sadahito Aoshima

      Article first published online: 2 SEP 2013 | DOI: 10.1002/pola.26907

      Thumbnail image of graphical abstract

      The first example of the living cationic polymerization of a vinylnaphthalene derivative is reported. The reaction has been regarded as difficult because of the uncontrollable side reactions caused by the high electron density of aromatic rings in these compounds. In this study, successful living polymerization was demonstrated for 6-tert-butoxy-2-vinylnaphthalene and 6-acetoxy-2-vinylnaphthalene using a TiCl4/SnCl4 combined initiating system in the presence of ethyl acetate as an added base at−30°C.

    13. Statistical copolymers of norbornene and 5-vinyl-2-norbornene by a ditungsten complex mediated ring-opening metathesis Polymerization: Synthesis, thermal properties, and kinetics of thermal decomposition (pages 4835–4844)

      Georgios Floros, Fotini Agrafioti, Alexios Grigoropoulos, Patrina Paraskevopoulou, Konstantinos Mertis, Maria Tseklima, Maria Veli and Marinos Pitsikalis

      Article first published online: 16 SEP 2013 | DOI: 10.1002/pola.26909

      Thumbnail image of graphical abstract

      Statistical copolymers of norbornene with 5-vinyl-2-norbornene were prepared by ring-opening metathesis polymerization, employing the triply bonded ditungsten complex Na[W2(μ-Cl)3Cl4(THF)2]·(THF)3. Structural parameters of the copolymers were calculated, and their thermal properties were thoroughly studied.

    14. Facile synthesis of soluble aromatic poly(amide amine)s via C–N coupling reaction: Characterization, thermal, and optical properties (pages 4845–4852)

      Guanjun Chang, Li Yang, Junxiao Yang, Yawen Huang, Ke Cao, Lin Zhang and Runxiong Lin

      Article first published online: 10 SEP 2013 | DOI: 10.1002/pola.26910

      Thumbnail image of graphical abstract

      Two soluble and high-thermal stability aromatic poly(amide amine)s are successfully synthesized by a Pd-catalyzed polycondensation, exhibiting significantly different photonic luminescence and electroactivity.

    15. Facile synthesis of polymer–peptide conjugates via direct amino acid coupling chemistry (pages 4853–4859)

      Gwen F. Chimonides, Arun A. Sohdi, Mohammad R. Khaleghi, Claire R. Hurley, Dave J. Adams and Paul D. Topham

      Article first published online: 16 SEP 2013 | DOI: 10.1002/pola.26913

      Thumbnail image of graphical abstract

      Polymer-peptide conjugates of varying molecular compositions are synthesized in a simple, industrially viable manner. The reported route combines a low number of synthetic steps with a high yield and a straightforward purification. Chloroformate coupling is shown to be the most efficient route when compared with carbodiimide and phosphonium chemistries.

    16. All-donor poly(arylene-ethynylene)s containing anthracene and silole-based units: Synthesis, electronic, and photovoltaic properties (pages 4860–4872)

      Roberto Grisorio, Gian Paolo Suranna, Piero Mastrorilli, Giovanni Allegretta, Anna Loiudice, Aurora Rizzo, Giuseppe Gigli, Kyriaki Manoli, Maria Magliulo and Luisa Torsi

      Article first published online: 18 SEP 2013 | DOI: 10.1002/pola.26914

      Thumbnail image of graphical abstract

      Four new all-donor poly(arylene-ethynylene)s obtained by the combination of silole-based and 9,10-diethynyl-anthracene units were synthesized and fully characterized, in order to draw the appropriate structure–property relationships. As a result of its suitable light-harvesting properties, hole mobility, and PC61BM/polymer interactions, the dithienosilole-based polymer DTSA exhibited the highest performances in bulk heterojunction solar cells (1.50%), representing one of the best results for all-donor polymer-based devices constructed without the use of additives or annealing processes.

    17. Cationic copolymerization of racemic-β-butyrolactone with L,L-lactide: One-pot synthesis of block copolymers (pages 4873–4884)

      Malgorzata Basko, Andrzej Duda, Slawomir Kazmierski and Przemyslaw Kubisa

      Article first published online: 30 SEP 2013 | DOI: 10.1002/pola.26916

      Thumbnail image of graphical abstract

      Block copolymers of β-butyrolactone (BL) and l,l-lactide (LA) were obtained by the cationic polymerization in the presence of alcohol. It was shown that polymerization proceeded in sequential manner, with poly-BL formed at the first stage acting as a macroinitiator for the subsequent polymerization of LA. The blocky structure of copolymers was confirmed by NMR, thermogravimetric analysis, and gel permeation chromatography. The proposed mechanism of copolymerization was supported by following the changes of the 1H NMR chemical shift of the acidic proton.

    18. Novel phenanthrocarbazole based donor–acceptor random and alternating copolymers for photovoltaics (pages 4885–4893)

      Zhiqiang Deng, Lie Chen and Yiwang Chen

      Article first published online: 10 SEP 2013 | DOI: 10.1002/pola.26917

      Thumbnail image of graphical abstract

      A series of random copolymers and corresponding alternating copolymers based on 6H-phenanthro[1,10,9,8-cdefg]carbazole (PC) are synthesized for bulk heterojunction polymer solar cells. The band gap and energy levels of the PC-based copolymers are well-modulated by varying the feed ratio of the monomers. The efficiency of random copolymers with a donor/acceptor molar ratio of 2:1 are close to that of alternating analogue-based devices by using PCBM as the acceptor. With the advantages of easy synthesis and convenient molecular modulation, the random copolymer is believed to be promising in the development of low band gap polymers for photovoltaics.

    19. Renewable benzoxazine monomers from “lignin-like” naturally occurring phenolic derivatives (pages 4894–4903)

      Marc Comí, Gerard Lligadas, Juan C. Ronda, Marina Galià and Virginia Cádiz

      Article first published online: 16 SEP 2013 | DOI: 10.1002/pola.26918

      Thumbnail image of graphical abstract

      Renewable benzoxazine monomers from “lignin-like” naturally occurring phenolic derivatives are presented. Benzoxazines of three naturally occurring phenylpropanoid phenols are described: ferulic, coumaric, and phloretic acids and their esters. The corresponding polybenzoxazines were prepared thermally and characterized by differential scanning calorimetry and thermogravimetric analysis techniques.

    20. (N-Heterocyclic carbene)Pd(triethylamine)Cl2 as precatalyst for the synthesis of Poly(triarylamine)s (pages 4904–4911)

      Reiner Sebastian Sprick, Mario Hoyos, Ming-Tsz Chen, Michael Lewis Turner and Oscar Navarro

      Article first published online: 18 SEP 2013 | DOI: 10.1002/pola.26919

      Thumbnail image of graphical abstract

      The use of a highly active, air- and moisture-stable N-heterocyclic carbene-palladium(II) complex is presented for the polymerization of primary amines and aryl dibromides and dichlorides by Buchwald–Hartwig coupling. In comparison to previous catalytic systems, higher molecular weight polymers with improved yields were obtained in shorter reaction times.

    21. In situ monitoring the thermal degradation of PCPDTBT low band gap polymers with varying alkyl side-chain patterns (pages 4912–4922)

      Lidia Marin, Huguette Penxten, Sarah Van Mierloo, Robert Carleer, Laurence Lutsen, Dirk Vanderzande and Wouter Maes

      Article first published online: 18 SEP 2013 | DOI: 10.1002/pola.26920

      Thumbnail image of graphical abstract

      The degradation pattern of a series of low band gap PCPDTBT polymers under thermal stress is investigated by a combination of in situ spectroscopic and thermal analysis techniques (UV-visible, Fourier transform-IR, thermogravimetric analysis, thermogravimetry-thermal desorption-gas chromatography/mass spectrometry). The influence of the side chains and the synthetic history on the thermal stability is related to the application of these materials in organic photovoltaics.

    22. Preparation of amphiphilic diblock copolymers with pendant hydrophilic phosphorylcholine and hydrophobic dendron groups and their self-association behavior in water (pages 4923–4931)

      Kazuki Osawa, Toyoko Imae, Masaki Ujihara, Atsushi Harada, Kanako Ochi, Kazuhiko Ishihara and Shin-ichi Yusa

      Article first published online: 16 SEP 2013 | DOI: 10.1002/pola.26921

      Thumbnail image of graphical abstract

      A generation 3.5 poly(amido amine) dendron containing a 16 n-butyl terminal group-bearing acrylamide monomer (AaUG3.5) was prepared. AaUG3.5 was polymerized using the poly(2-methacryloyloxyethyl phosphorylcholine) (pMPC)-based macrochain transfer agent via reversible addition–fragmentation chain transfer radical polymerization to obtain amphiphilic diblock copolymers (pMPC-b-pAaUG3.5) with different compositions. pMPC-b-pAaUG3.5 formed vesicles or large compound micelles depending on the composition.

    23. Remarkably stable amphiphilic random copolymer assemblies: A structure–property relationship study (pages 4932–4943)

      Krishna Dan, Priya Rajdev, Jolly Deb, Siddhartha S. Jana and Suhrit Ghosh

      Article first published online: 11 SEP 2013 | DOI: 10.1002/pola.26922

      Thumbnail image of graphical abstract

      A reactive prepolymer-based route generated highly biocompatible amphiphilic random copolymers with different hydrophilic segments, while maintaining all other structural parameters. They show highly stable aggregation in an aqueous medium. Hydrophilic chain length determines the nature of the aggregates, their dye encapsulation efficiency, and properties at lower critical solution temperature. Shorter chains show thermoresponsive multimicellar cluster formation with less efficient dye encapsulation, while the longer, hydrophilic, chain-containing polymers form vesicles with more efficient encapsulation properties for both hydrophobic and hydrophilic dye.

SEARCH

SEARCH BY CITATION