Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 52 Issue 12

15 June 2014

Volume 52, Issue 12

Pages i–iv, 1643–1770

  1. Cover Image

    1. Top of page
    2. Cover Image
    3. Articles
    1. You have free access to this content
      Cover Image, Volume 52, Issue 12 (pages i–ii)

      Article first published online: 6 MAY 2014 | DOI: 10.1002/pola.27225

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      A series of highly fluorinated poly(phthalazinone ether)s with high molecular weights based on AB-type monomers are synthesized by self-condensation polymerizations, as presented by Xiuhua Li, Yan Gao, Qiang Long, and Allan S. Hay on page 1761 (DOI: 10.1002/pola.27199). The structure and properties of the fluorinated poly(phthalazinone ether)s are tuned by side groups of the AB-type monomers. The polymers have very high glass transition temperatures (Tg) varying from 337 to 349 °C and show excellent solubility, thermal stability, mechanical properties, high water contact angles, and absorption edges below 340 nm.

    2. You have free access to this content
      Cover Image, Volume 52, Issue 12 (pages iii–iv)

      Article first published online: 6 MAY 2014 | DOI: 10.1002/pola.27226

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      On page 1737 (DOI: 10.1002/pola.27175), Chang-Feng Li, Qi-Kai Zhang, Hai-Jian Tian, Chun-Peng Chai, Long-Cheng Gao, Zhihao Shen, Xing-He Fan, and Yun-Jun Luo report the synthesis of polydimethylsiloxane-based rod-coil-rod triblock copolymers using nitroxide mediated radical polymerization. SAXS and TEM results demonstrate that the triblock copolymers form lamellar structures. Upon heating, the blocks become liquid crystalline within the lamellar structures of the block copolymers, resulting in hierarchically ordered structures. These triblock copolymers are potentially useful as thermoplastic liquid crystal elastomers due to their distinctly different glass transition temperatures.

  2. Articles

    1. Top of page
    2. Cover Image
    3. Articles
    1. Hyperbranched aliphatic polyether esters by ring-opening polymerization of epoxidized 2-hydroxyethyl methacrylate (pages 1643–1651)

      Xinhua Huang, Min Seon Heo, Jin-Wook Yoo, Jin-Seok Choi and Il Kim

      Article first published online: 14 APR 2014 | DOI: 10.1002/pola.27182

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      A series of well-defined hyperbranched polyether esters comprised of ether and ester backbones and multiple hydroxyl groups on the core and periphery exhibit good degradability and low cytotoxicity, resulting in an ideal candidate material for biomedical applications.

    2. Spotlight Article

      Low band-gap D–A conjugated copolymers based on anthradithiophene and diketopyrrolopyrrole for polymer solar cells and field-effect transistors (pages 1652–1661)

      Jun Huang, Yongxiang Zhu, Lianjie Zhang, Ping Cai, Xiaofeng Xu, Junwu Chen and Yong Cao

      Article first published online: 25 MAR 2014 | DOI: 10.1002/pola.27163

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      Conjugated copolymers PADT-DPP and PADT-FDPP based on anthradithiophene (ADT) and diketopyrrolopyrrole (DPP), with thiophene and furan as the π-conjugated bridge, respectively, were synthesized. The two polymers exhibit broad absorption ranges with band gaps of 1.44 eV and 1.50 eV, respectively. PADT-DPP showed a better efficiency of 3.46% in polymer solar cell and a higher field-effect hole mobility of 4.7 × 10−3 cm2/(V s).

    3. Improved synthesis of oligomeric phthalonitriles and studies designed for low temperature cure (pages 1662–1668)

      Matthew Laskoski, Arianna Neal, Teddy M. Keller, Dawn Dominguez, Christopher A. Klug and Andrew P. Saab

      Article first published online: 25 MAR 2014 | DOI: 10.1002/pola.27161

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      An improved synthetic method has been developed for oligomeric aromatic ether ketone-based phthalonitrile (PN) resins. A new curing additive was studied and was found to lower the cure temperature of the PN resin to around 150 ° C. The mechanical and thermooxidative properties were compared for both cure systems.

    4. A rheological and spectroscopic study on the kinetics of self-healing in a single-component diels–alder copolymer and its underlying chemical reaction (pages 1669–1675)

      Ranjita K. Bose, Julia Kötteritzsch, Santiago J. Garcia, Martin D. Hager, Ulrich S. Schubert and Sybrand van der Zwaag

      Article first published online: 1 APR 2014 | DOI: 10.1002/pola.27164

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      Self-healing polymers based on reversible Diels–Alder chemistry were synthesized along with nonhealing control polymers. A combined FTIR and rheological study showed that reversible crosslinking of the network can be achieved, which was linked to bulk microscratch healing. The use of nonhealing control samples did show some viscoelastic recovery but lacked chemical reversibility. Therefore, care must be taken to distinguish molecular healing from viscoelastic recovery; this can be achieved by combined spectroscopic and mechanical investigations.

    5. Dual stimuli-responsive microgels based on photolabile crosslinker: Temperature sensitivity and light-induced degradation (pages 1676–1685)

      Shanshan Bian, Jin Zheng and Wuli Yang

      Article first published online: 25 MAR 2014 | DOI: 10.1002/pola.27165

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      A new ortho-nitrobenzyl-based crosslinker is synthesized through a convenient route. Dual stimuli-responsive P(VCL-co-NHMA) microgels based on the new photolabile crosslinker, with uniform size and fine morphology are successfully prepared by precipitation polymerization. The microgels perform at higher volume phase transition temperature with increasing N-hydroxymethyl acrylamide (NHMA) content and can totally degrade into short linear polymers by UV light. Increasing light intensity results in a faster degradation. Thus, the degradation rate of microgels can be controlled by changing light properties, which may indicate the potential application in some fields.

    6. A novel low-bandgap conjugated polymer based on Ru(II) bis(acetylide) complex and BODIPY moieties (pages 1686–1692)

      Shuwei Zhang, Yuan Sheng, Guo Wei, Yiwu Quan, Yixiang Cheng and Chengjian Zhu

      Article first published online: 1 APR 2014 | DOI: 10.1002/pola.27166

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      A novel conjugated polymer P-1 with Ru(II) complex and BODIPY moieties in the main chain was synthesized by Pd-catalyzed Sonogashira coupling reactions. Compared with the reference polymer P-2 without Ru(II) complex moieties, P-1 shows obviously lower bandgap, as shown by cyclic voltammetry (CV) and DFT calculations, which is as low as 0.87 eV. P-1 also appears redshifted both in absorption and fluorescence spectra.

    7. Resorcinol-based benzoxazine with low polymerization temperature (pages 1693–1699)

      Andre Arnebold, Oliver Schorsch, Johannes Stelten and Andreas Hartwig

      Article first published online: 29 MAR 2014 | DOI: 10.1002/pola.27169

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      A new reactive resorcinol-based benzoxazine (R-a) exhibits relatively low self-polymerization temperature compared to common benzoxazines like BA-a. The use of thermolatent super acids as initiators lead to a futher decrease in curing temperature. Furthermore, the combination of R-a and a thermolatent initiator features long shelf-life and makes it therefore to a suitable system for technical applications.

    8. Accelerated brush growth on nanoparticle surfaces by reversible addition-fragmentation chain transfer polymerization (pages 1700–1705)

      Yang Jiao and Pinar Akcora

      Article first published online: 1 APR 2014 | DOI: 10.1002/pola.27170

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      Unusual kinetic results are presented for achieving grafted chain lengths longer than the free chains using RAFT polymerization. Surface initiated polymerization grows faster than the free chains in solution with high RAFT agent coverage (1.95 agents/nm2) on nanoparticles. Activation of the anchored CTA is limited by the diffusion of macro-radicals within the growing grafts. Thus, the radical transfer and exchange reactions become inefficient between grafts and free polymer, and convert the surface-initiated RAFT mechanism to a free radical polymerization.

    9. Thermoresponsive dendronized polymeric sensors (pages 1706–1713)

      Lianxiao Liu, Wen Li, Jiatao Yan and Afang Zhang

      Article first published online: 2 APR 2014 | DOI: 10.1002/pola.27171

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      Thermoresponsive dendronized copolymers carrying dendritic oligoethylene glycol (OEG) scaffolds and solvatochromic dye pendants are synthesized, and their aqueous solution colors varied according to temperature and solution pH. Dendritic OEGs are found to capture the dye moieties, which can be enhanced with the increase of dendron generation and solution temperature, but retarded above their phase transition temperatures. The dye transition within the collapsed polymer media is governed by the thickness of dendronized polymers.

    10. Radical copolymerization of chlorotrifluoroethylene with 4-bromo-3,3,4,4-tetrafluorobut-1-ene (pages 1714–1720)

      Gérald Lopez, Noureddine Ajellal, Alagappan Thenappan and Bruno Ameduri

      Article first published online: 1 APR 2014 | DOI: 10.1002/pola.27172

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      A wide range of poly(CTFE-co-BTFB) copolymers are prepared by radical copolymerization of chlorotrifluoroethylene (CTFE) with 3,3,4,4-tetrafluoro-4-bromobut-1-ene (BTFB). Their microstructures are determined by means of NMR spectroscopy and elemental analysis. These copolymers exhibit fair to satisfactory thermal stability as well as an alternating character for increased amount of BTFB incorporated in the copolymer. These original fluoropolymers with reactive pendant brominated groups are suitable candidates for various applications.

    11. Synthesis of methallylic monomers bearing ammonium side-groups and their radical copolymerization with chlorotrifluoroethylene (pages 1721–1729)

      Ali Alaaeddine, Frédéric Boschet and Bruno Ameduri

      Article first published online: 1 APR 2014 | DOI: 10.1002/pola.27173

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      Methallylic monomers bearing triethyl or one or two 4-diazabicyclo[2.2.2]octane (DABCO) ammonium side-groups are prepared and copolymerized with chlorotrifluoroethylene. Several copolymerization parameters (nature and amounts of initiators, solvent, and temperature) are investigated. In all cases, chlorotrifluoroethylene is more reactive than the methallylic monomers. These copolymers are stable up to 180 °C without any degradation and have a decomposition temperature (Td,10%) above 300 ° C. Finally, their ionic exchange capacities (IECs) range between 0.94 and 1.69meq g−1.

    12. Spotlight Article

      Chain-growth condensation polymerization approach to synthesis of well-defined polybenzoxazole: Importance of higher reactivity of 3-amino-4-hydroxybenzoic acid ester compared to 4-amino-3-hydroxybenzoic acid ester (pages 1730–1736)

      Yoshihiro Ohta, Tetsurou Niiyama, Akihiro Yokoyama and Tsutomu Yokozawa

      Article first published online: 2 APR 2014 | DOI: 10.1002/pola.27174

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      Well-defined poly(o-hydroxyamide) was synthesized by chain-growth condensation polymerization of phenyl 4-{(2-methoxyethoxy)methoxy(MEM-oxy)}-3-{(4-octyloxybenzyl) (OOB) amino}benzoate with an initiator, followed by removal of the MEM and OOB groups with trifluoroacetic acid. Cyclodehydration of poly(o-hydroxyamide) proceeded at 350 °C to yield polybenzoxazole, which was insoluble in organic solvents and acids.

    13. Hierarchically ordered ABA triblock copolymer with large difference in glass transition temperatures of the two blocks (pages 1737–1744)

      Chang-Feng Li, Qi-Kai Zhang, Hai-Jian Tian, Chun-Peng Chai, Long-Cheng Gao, Zhihao Shen, Xing-He Fan and Yun-Jun Luo

      Article first published online: 2 APR 2014 | DOI: 10.1002/pola.27175

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      The rod-coil-rod triblock copolymers, (PMVBP-b-PDMS-b-PMVBP), were synthesized by nitroxide-mediated radical polymerization. SAXS and TEM results demonstrate that the triblock copolymers form lamellar structures. Upon heating to the temperature at which the LC phase of PMVBP forms, the PMVBP blocks become liquid crystalline within the lamellar structures of the BCPs, resulting in hierarchically ordered structures. These triblock copolymers are potentially useful as thermoplastic LC elastomers owing to their distinctly different glass transition temperatures.

    14. Spotlight Article

      Dynamic control of volume phase transitions of poly(N-isopropylacrylamide) based microgels in water using hydrazide-aldehyde chemistry (pages 1745–1754)

      Yunhua Chen, Nicholas Ballard, Oliver D. Coleman, Ian J. Hands-Portman and Stefan A. F. Bon

      Article first published online: 7 APR 2014 | DOI: 10.1002/pola.27177

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      The volume phase transition temperature (VPTT) of copolymer microgel particles made from N-isopropylacrylamide (NIPAm) and methacryloyl hydrazide (MH) can be tailored upon reaction of the hydrazide functional group with aldehydes. The reversibility of the hydrazone formation and dynamic control of the thermo-responsive behavior of the microgels were clearly demonstrated by using hydrophilic and hydrophobic aldehydes.

    15. Synthesis and property of polyoxazolidone having fluorene moiety by polyaddition of diisocyanate and diepoxide (pages 1755–1760)

      Motohisa Azechi and Takeshi Endo

      Article first published online: 7 APR 2014 | DOI: 10.1002/pola.27181

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      Polyoxazolidones with fluorenyl groups were synthesized from 9,9-diglycidyl fluorene and various diisocyanates. The IR spectrum of the obtained polymer showed absorption in carbonyl region, indicating the formation of the expected oxazolidone moieties along with isocyanurate moieties via cyclotrimerization. As a result of polyaddition, the formation of isocyanurate could be controlled.

    16. Synthesis and characterization of highly fluorinated poly(phthalazinone ether)s based on AB-type monomers (pages 1761–1770)

      Xiuhua Li, Yan Gao, Qiang Long and Allan S. Hay

      Article first published online: 22 APR 2014 | DOI: 10.1002/pola.27199

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      A series of highly fluorinated poly(phthalazinone ether)s with high-molecular weights based on AB-type monomers containing methyl or phenyl side groups have been successfully synthesized by nucleophilic addition–elimination reactions and following self-condensation polymerization. The polymers have very high Tgs varying from 337 to 349 °C and show excellent solubility, thermal stability, mechanical properties, high-water contact angles, and absorption edges below 340 nm. These results indicate that the polymers are promising as high-performance materials.

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