Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 53 Issue 1

1 January 2015

Volume 53, Issue 1

Pages i–iv, 1–132

  1. Cover Image

    1. Top of page
    2. Cover Image
    3. Rapid Communications
    4. Articles
    1. You have free access to this content
      Cover Image, Volume 53, Issue 1 (pages i–ii)

      Article first published online: 25 NOV 2014 | DOI: 10.1002/pola.27474

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      On page 15 (DOI: 10.1002/pola.27442), Sven Nietzel, Daejune Joe, Joseph W. Krumpfer, Frank Schellenberger, Abdulhamid A. Alsaygh, Gerhard Fink, Markus Klapper, and Klaus Müllen introduce a fragmentable organic support material for Ziegler-Natta catalysts based on micrometer-sized aggregates of polystyrene nanoparticles, producing high-density polyethylene with medium molecular weight distributions (MWDs = 3–4). The fragmentation behavior of dye-labeled support aggregates into the initial nanoparticles is demonstrated using laser scanning confocal fluorescence microscopy (LSCFM) as a nondestructive method. The cover image shows LSCFM images of the initial support and the obtained product beads of ethylene polymerizations terminated at 2.5, 7.5 and 15 min.

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      Cover Image, Volume 53, Issue 1 (pages iii–iv)

      Article first published online: 25 NOV 2014 | DOI: 10.1002/pola.27475

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      This TE micrograph shows silica nanoparticles functionalized with a slightly interconnected bifunctional RAFT agent. On page 103 (DOI: 10.1002/pola.27454), Dennis Huebner, Vanessa Koch, Bastian Ebeling, Jannik Mechau, Judith Elisabeth Steinhoff, and Philipp Vana report the systematic study of the immobilization of RAFT agents on silica for surface-initiated RAFT polymerizations. The dependence of the functionality of the RAFT-agent anchor group is also examined. Monoalkoxy-, dialkoxy-, and trialkoxy silyl ether groups are incorporated in trithiocarbonate-type RAFT agents and are bound to planar silica surfaces as well as to silica nanoparticles. The immobilization efficiency and structure of the bound RAFT-agent film varies strongly depending on the solvent and the anchor group functionality.

  2. Rapid Communications

    1. Top of page
    2. Cover Image
    3. Rapid Communications
    4. Articles
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      Hydrolytically stable polyurethanes (pages 1–4)

      Jungmee Kang and Joseph P. Kennedy

      Article first published online: 27 OCT 2014 | DOI: 10.1002/pola.27447

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      Polyisobutylene-based polyurethanes (PU) exhibit outstanding hydrolytic stability. PU samples were immersed in PBS at pH 7.4 and aqueous buffers at pH 1 and 11, and then heated at 85 °C for 10 weeks. According to SEC analysis, Mn, Mw, Mw/Mn did not change (within experimental variation) in the course of the test. In contrast, a PDMS-based PU severely degraded after one week under the same conditions.

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      Synthesis of amino-containing syndiotactic polystyrene as efficient polymer support for palladium nanoparticles (pages 5–9)

      Zhenghai Shi, Fang Guo, Yang Li and Zhaomin Hou

      Article first published online: 7 NOV 2014 | DOI: 10.1002/pola.27455

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      Amino-containing functionalized syndiotactic polystyrenes with high melting temperatures and temperature stability are synthesized by the direct polymerization of amino-containing styrenic monomers in the presence of a half-sandwich scandium catalyst system [(C5Me4SiMe3)Sc(CH2C6H4NMe2-o)2]/[Ph3C][B(C6F5)4]. The high syndiotactic poly(N,N-dimethylamino)styrene (rrrr > 99%), then used as novel polymer supports, effectively anchored Pd nanoparticles (3 wt % of Pd) with a diameter of 4 or 5 nm that were uniformly dispersed on polymer matrix.

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      Stabilization of factor VIII by poly(2-oxazoline) hydrogels (pages 10–14)

      Matthias Hartlieb, Stephanie Schubert, Kristian Kempe, Norbert Windhab and Ulrich S. Schubert

      Article first published online: 18 NOV 2014 | DOI: 10.1002/pola.27457

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      Using a bis-functional monomer, poly(2-oxazoline) hydrogels were synthesized via cationic ring-opening polymerization and used to stabilize FVIII in aqueous solution.

  3. Articles

    1. Top of page
    2. Cover Image
    3. Rapid Communications
    4. Articles
    1. Spotlight Article

      Organic nanoparticles as fragmentable support for Ziegler–Natta catalysts (pages 15–22)

      Sven Nietzel, Daejune Joe, Joseph W. Krumpfer, Frank Schellenberger, Abdulhamid A. Alsaygh, Gerhard Fink, Markus Klapper and Klaus Müllen

      Article first published online: 29 OCT 2014 | DOI: 10.1002/pola.27442

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      Micrometer-sized aggregates of polystyrene nanoparticles are presented as organic support materials for Ziegler–Natta catalysts. The catalytic activity in ethylene slurry polymerizations is found to be directly correlated to the hydroxyl group content of the supports. The ability to produce medium molecular weight distributions of high-density polyethylene in a one-pot, one-catalyst process in conjunction with good support fragmentability is demonstrated.

    2. Synthesis via ATRP, kinetics study and characterization (molecular-morphological) of 3-Arm star diblock copolymers of the (PS-b-P2VP)3 type (pages 23–32)

      George Polymeropoulos, Dimitrios Moschovas, Anastasia Kati, Apostolos Karanastasis, Styliani Pelekanou, Panagiotis Christakopoulos, Georgios Sakellariou and Apostolos Avgeropoulos

      Article first published online: 18 OCT 2014 | DOI: 10.1002/pola.27432

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      The successful synthesis via ATRP of 3-arm star homopolymers and corresponding diblock copolymers of the (PS)3 and (PS-b-P2VP)3 types, through an initiator bearing three –Br groups, is discussed. A kinetics study is performed for the synthesis of the star homopolymer to evaluate polymerization time versus polydispersity, molecular weight, and yield. Molecular characterization through various techniques verifies the preparation of both architectures and TEM studies confirm the microphase separation of the final copolymers.

    3. Dynamic covalent polypeptides showing tunable secondary structures and thermoresponsiveness (pages 33–41)

      Jiatao Yan, Kun Liu, Xiuqiang Zhang, Wen Li and Afang Zhang

      Article first published online: 19 OCT 2014 | DOI: 10.1002/pola.27433

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      The imine condensation from poly(l-lysine)s and oligoethylene glycol (OEG)-based dendritic aldehydes afforded dynamic OEGylated polypeptides, which show enhanced helical conformation and superior thermoresponsive properties. Their phase transition temperatures were governed predominately by terminal groups and coverage of OEG dendrons, and could be tuned simply by varying ratios of OEG dendrons with different hydrophilicity. Furthermore, thermally induced dehydration and aggregation was found to enhance the imine formation and, at the same time, to switch helical conformations of polypeptides.

    4. Iron complexes as photoinitiators for radical and cationic polymerization through photoredox catalysis processes (pages 42–49)

      Jing Zhang, Damien Campolo, Frederic Dumur, Pu Xiao, Jean Pierre Fouassier, Didier Gigmes and Jacques Lalevée

      Article first published online: 23 OCT 2014 | DOI: 10.1002/pola.27435

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      A series of iron complexes (FeCs) were developed and applied as photocatalysts in photoinitiating systems for radical and cationic polymerization. These FeC-based systems exhibit photocatalytic properties, undergo the formation of radicals, radical cations, and cations, and can operate through oxidation or/and reduction cycles. These reported systems are characterized by an unprecedented reactivity on LED irradiation. Contrary to the most famous reference system (BAPO), the newly developed systems with very low FeC content (0.02 wt %) are still highly efficient in photopolymerization, illustrating the performance of the proposed catalytic approach.

    5. Spotlight Article

      ROMP synthesis of novel thermo-, pH-, and salt-responsive (co)polymers containing the morpholino functional group (pages 50–58)

      Johannes A. van Hensbergen, Sylvia Ganda, Peter J. Roth, Robert P. Burford and Andrew B. Lowe

      Article first published online: 21 OCT 2014 | DOI: 10.1002/pola.27436

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      A series of new (co)polymers containing the multiresponsive morpholino functional group have been prepared by ring-opening metathesis polymerization (ROMP) with RuCl2(PCy3)2CHPh.

    6. Using controlled radical polymerization to confirm the lower critical solution temperature of an N-(alkoxyalkyl) acrylamide polymer in aqueous solution (pages 59–67)

      Xeniya Savelyeva, Lucia Li and Milan Marić

      Article first published online: 21 OCT 2014 | DOI: 10.1002/pola.27437

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      Poly[N-(3-methoxypropyl)] acrylamide (MPAM) homopolymers and block copolymers with N,N-diethylacrylamide (DEAAM) as a second block were synthesized and well controlled by controlled radical polymerization methods, particularly RAFT. The solution properties were assessed by UV–Vis and dynamic light scattering. Dual lower critical solution temperature type behavior was found for the block copolymers and the cloud point temperature of poly(MPAM) was determined to be about 73–92 °C, depending on molecular weight and solution concentration.

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      Preparation, properties, and antibacterial behavior of a novel cellulose derivative containing lactam groups (pages 68–78)

      Fanny Joubert, Gary J. Sharples, Osama M. Musa, David R. W. Hodgson and Neil R. Cameron

      Article first published online: 29 OCT 2014 | DOI: 10.1002/pola.27441

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      A novel cellulose derivative is prepared by the chemical modification of hydroxyethyl cellulose with pyrrolidone groups. The new material has improved solubility, lower solution viscosity, and enhanced thermal stability compared with hydroxyethyl cellulose as well as some antibacterial properties.

    8. Influence of branching on the chiral self-assembly of poly(phenylene ethynylene) (pages 79–84)

      Joost Steverlynck, Pieter Leysen and Guy Koeckelberghs

      Article first published online: 27 OCT 2014 | DOI: 10.1002/pola.27443

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      A series of all-conjugated poly(phenylene ethynylenes) with a controllable degree of branching was prepared. The influence of branching on the self-assembly was studied using UV–Vis, CD, fluorescence spectroscopy and DSC. Also studied were the effects of that branching, and the resulting change in self-assembly, on the chiral expression.

    9. Ordered nanostructures from self-assembly of H-shaped coil–rod–coil molecules (pages 85–92)

      Zhuoshi Wang, Keli Zhong, Yongri Liang, Tie Chen, Bingzhu Yin, Myongsoo Lee and Long Yi Jin

      Article first published online: 27 OCT 2014 | DOI: 10.1002/pola.27448

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      H-shaped coil–rod–coil oligomers, consisting of biphenyl, phenylene vinylene, and phenylene ethynylene units as the rigid segment have been synthesized. The experimental results reveal that the lateral methyl groups attached to the surface of the rod and coil segments dramatically influence the formation of various supramolecular nanostructures in the crystalline phase.

    10. Design, polymerization, and properties of polyurethane elastomers from miscible, immiscible, and hybridized seed-oil derived soft segment blends (pages 93–102)

      Mark F. Sonnenschein, Valeriy V. Ginzburg, Adam L. Grzesiak, Klaus Schiller and Benjamin L. Wendt

      Article first published online: 10 NOV 2014 | DOI: 10.1002/pola.27450

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      Polyol soft segments can be blended but phase separate if mixing thermodynamics are unfavorable. This is particularly evident in attempts to blend seed-oil polyols with some conventional petrochemical polyols. Polyurethane elastomers from phase separated polyols have broad glass transitions and poor tensile properties. Seed-oil soft segment blends that are chosen for miscibility, or are chemically polymerized forming a single soft segment can result in high-performing elastomers with narrow glass transitions and good tensile properties.

    11. Comparison of monomethoxy-, dimethoxy-, and trimethoxysilane anchor groups for surface-initiated RAFT polymerization from silica surfaces (pages 103–113)

      Dennis Huebner, Vanessa Koch, Bastian Ebeling, Jannik Mechau, Judith Elisabeth Steinhoff and Philipp Vana

      Article first published online: 7 NOV 2014 | DOI: 10.1002/pola.27454

      Thumbnail image of graphical abstract

      The immobilization of RAFT agents on silica for surface-initiated RAFT polymerizations was studied systematically in dependence on the functionality of the RAFT-agent anchor group. Monoalkoxy-, dialkoxy-, and trialkoxy silyl ether groups were incorporated into trithiocarbonate-type RAFT agents and bound to planar silica surfaces as well as to silica nanoparticles. The immobilization efficiency and the structure of the bound RAFT-agent film varied strongly in dependence on the solvent and the anchor group functionality.

    12. pH-responsive near-infrared emitting conjugated polymer nanoparticles for cellular imaging and controlled-drug delivery (pages 114–122)

      Jousheed Pennakalathil, Alp Özgün, Irem Durmaz, Rengül Cetin-Atalay and Dönüs Tuncel

      Article first published online: 17 NOV 2014 | DOI: 10.1002/pola.27458

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      pH-Responsive near-infrared emitting conjugated polymer nanoparticles (CPNs) were prepared, characterized, and their stabilities were investigated under various conditions. It was shown that CPNs can be effectively utilized as vehicles for pH-triggered release of anticancer drugs and for cellular imaging.

    13. Isobutylene-rich macromonomers: Dynamics and yields of peroxide-initiated crosslinking (pages 123–132)

      Jackson M. Dakin, Karthik Vikram Siva Shanmugam, Christopher Twigg, Ralph A. Whitney and J. Scott Parent

      Article first published online: 17 NOV 2014 | DOI: 10.1002/pola.27462

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      Peroxide-initiated crosslinking dynamics and yields of a range of isobutylene-rich macromonomers are examined and discussed.

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