Journal of Polymer Science Part A: Polymer Chemistry

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

1 May 2013

Volume 51, Issue 9

Pages 1–2109

  1. Cover Image

    1. Top of page
    2. Cover Image
    3. Rapid Communication
    4. Articles
    5. Notes
    1. You have free access to this content
      Cover Image, Volume 51, Issue 9 (pages i–ii)

      Article first published online: 25 MAR 2013 | DOI: 10.1002/pola.26658

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      The image describes the electrochromic properties of dithienothiophene and benzotriazole containing donor-acceptor type conjugated polymers. The study by Ali Cirpan et al. on page 1933 indicates that incorporating dithienothiophene into the structure leads to fast switching times compared to benzotriazole based polymers, as well as competent percent transmittance in the near-IR region. Both polymers are multichromic, ambipolar, and spray processable, making them suitable for electrochromic and low-cost flexible display device technology. Optical and electrochemical studies of the polymers show that these polymers can also be utilized in photovoltaic applications.

    2. You have free access to this content
      Inside Cover, Volume 51, Issue 9 (pages iii–iv)

      Article first published online: 25 MAR 2013 | DOI: 10.1002/pola.26659

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      Methacrylate based hard-soft-hard triblock copolymers show periodically well-organized morphologies, giving excellent actuation performances at relatively lower electric fields due to their polar methacrylate groups, lower modulus, and microstructures, which are superior to conventional SEBS/oil systems. As presented by Kie Yong Cho, Seung Sang Hwang, Ho Gyu Yoon, and Kyung-Youl Baek on page 1924, these highperformance soft actuator materials may find applications as artificial skin.

  2. Rapid Communication

    1. Top of page
    2. Cover Image
    3. Rapid Communication
    4. Articles
    5. Notes
    1. Biodegradable CO2-based polycarbonates with rapid and reversible thermal response at body temperature (pages 1893–1898)

      Qinghai Zhou, Lin Gu, Yonggang Gao, Yusheng Qin, Xianhong Wang and Fosong Wang

      Article first published online: 7 FEB 2013 | DOI: 10.1002/pola.26583

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      Thermoresponsive CO2-based biodegradable polycarbonates are designed and prepared. The lower critical solution temperature (LCST) can be quantitatively controlled within a temperature range covering physiological temperature, among which polycarbonate with a LCST of 36.3 °C (close to body temperature) is available.

  3. Articles

    1. Top of page
    2. Cover Image
    3. Rapid Communication
    4. Articles
    5. Notes
    1. Spotlight Article

      You have full text access to this OnlineOpen article
      Modeling controlled photodegradation in optically thick hydrogels (pages 1899–1911)

      Mark W. Tibbitt, April M. Kloxin and Kristi S. Anseth

      Article first published online: 7 FEB 2013 | DOI: 10.1002/pola.26574

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      A statistical-kinetic model of photodegradation is presented to describe light-induced property changes in photodegradable, crosslinked hydrogels. In this manner, spatial and temporal alterations to material properties can be quantified for photoresponsive hydrogels based on central physical parameters of the network. The model was applied to predict the degradation and erosion of PEGdiPDA hydrogels and predictions fit well with experimental data. In all, this model aids in understanding degradation and erosion behavior in photodegradable hydrogels and may be employed in the design of photoresponsive networks for a variety of applications.

    2. Design, synthesis, and self-assembly manipulating of polymerized ionic liquids contained imidazolium based on “Jacketing” effect (pages 1912–1923)

      Liang Weng, Jiao-Jiao Yan, He-Lou Xie, Guan-Qun Zhong, Si-Qi Zhu, Hai-Liang Zhang and Er-Qiang Chen

      Article first published online: 19 FEB 2013 | DOI: 10.1002/pola.26585

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      Polymerized ionic liquids (PILs) based on a “jacketing” effect containing imidazolium with different counter-anions were successfully designed and synthesized via radical polymerization. With a combined “jacketing” effect and appropriate interaction between the anions and cations, the whole molecular chain of PILs would be considered a hierarchical cylinder, and this cylinder can further form hexagonal columnar (ΦH) LC ordered structures.

    3. Electroactive methacrylate-based triblock copolymer elastomer for actuator application (pages 1924–1932)

      Kie Yong Cho, Seung Sang Hwang, Ho Gyu Yoon and Kyung-Youl Baek

      Article first published online: 19 FEB 2013 | DOI: 10.1002/pola.26563

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      A series of well-defined MMA-DMA-MMA triblock copolymers with different molecular weights and compositions were synthesized by in situ sequential block copolymerization of DMA followed by MMA from a difunctional initiator through Ru-based living radical polymerization. Obtained triblock copolymers showed periodically well-organized morphologies both in bulk and in film states, giving excellent actuation performances at relatively lower electric fields due to their polar methacrylate groups (k), lower modulus, and microstructures.

    4. Fused structures in the polymer backbone to investigate the photovoltaic and electrochromic properties of donor–acceptor-type conjugated polymers (pages 1933–1941)

      Sevki Can Cevher, Naime Akbasoglu Unlu, Ali Can Ozelcaglayan, Dogukan Hazar Apaydin, Yasemin Arslan Udum, Levent Toppare and Ali Cirpan

      Article first published online: 30 JAN 2013 | DOI: 10.1002/pola.26553

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      Benzotriazole- and dithienothiophene-based conjugated polymers were synthesized via Stille coupling. Electrochemical and optical properties of the polymers indicated that the polymers can be great candidates for photovoltaic and electrochromic applications. Therefore, spectroelectrochemical, cyclic voltammetry, and preliminary photovoltaic studies are performed and the results of the studies are highlighted.

    5. Constructing novel double-bond-containing well-defined amphiphilic graft copolymers via successive Ni-catalyzed living coordination polymerization and SET-LRP (pages 1942–1949)

      Yongjun Li, Guolin Lu, Bin Dai, Caixia Xu and Xiaoyu Huang

      Article first published online: 7 FEB 2013 | DOI: 10.1002/pola.26572

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      A series of well-defined amphiphilic graft copolymers, containing a hydrophobic double-bond-containing backbone and hydrophilic poly(2-(diethylamino)ethyl methacrylate) side chains, was constructed by the combination of Ni-catalyzed living coordination polymerization, SET-LRP, and the grafting-from strategy.

    6. Spotlight Article

      Microwave-assisted suzuki coupling reaction for rapid synthesis of conjugated polymer–poly(9,9-dihexylfluorene)s as an example (pages 1950–1955)

      Wensi Zhang, Ping Lu, Zhiming Wang and Yuguang Ma

      Article first published online: 19 FEB 2013 | DOI: 10.1002/pola.26573

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      Microwave-assisted (MA) Suzuki polymerization for polyfluorenes has been systematically investigated. It is very important to control the reaction conditions in order to depress the formation of cross-linked products. Compared with oil bath heating, MA synthesis can greatly reduce the reaction time from 48 h (oil bath heating) to 14 min, and resultant polymer products show the higher molecular weight of 40,000 under optimized conditions.

    7. A novel photo-acid generator bound molecular glass resist with a single protecting group (pages 1956–1962)

      Tatsuaki Kasai, Tomoya Higashihara and Mitsuru Ueda

      Article first published online: 7 FEB 2013 | DOI: 10.1002/pola.26575

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      A novel photo-acid generator (PAG) bound molecular glass photoresist with a single protecting group has been developed as a promising resist material for use in microelectronics.

    8. Poly(methyl methacrylate-co-pentaerythritol tetraacrylate-co-butyl methacrylate)-g-polystyrene: Synthesis and high oil-absorption property (pages 1963–1968)

      Ying Liang, Delong Liu and Hou Chen

      Article first published online: 6 FEB 2013 | DOI: 10.1002/pola.26576

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      High oil-absorption resin was successfully prepared via living radical polymerization on the surface of a polystyrene resin-supported N-chlorosulfonamide group utilizing MMA and BMA as monomers, FeCl3/IDA as the catalyst system, PETEA as a cross-linker, and VC as a reducing agent. The polymerization proceeded in a “living” manner as indicated by the linearity of the kinetic plot. The oil-absorption resin shows a toluene absorption capacity of 21 g g−1. The adsorption of oil behaves as a pseudo-first-orderkinetic model rather than a pseudo-second-order kinetic model.

    9. Three-arm star block copolymers of ε-caprolactone and acrylic acid: Synthesis and micellization behavior (pages 1969–1975)

      Jin-Xia Liu, Cong Yuan, Ze Su, Ting-Ting Xu, Liu-He Wei and Zhi Ma

      Article first published online: 19 FEB 2013 | DOI: 10.1002/pola.26577

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      Three-arm star poly(ε-caprolactone)-b-poly(acrylic acid) (T-A star PCL-b-PAA) copolymers were synthesized via a “core-first” approach combining ring-opening polymerization and atom transfer radical polymerization. GPC traces of copolymers produced showed that ROP of ε-CL and ATRP of tBuA in such a system were well controllable. The chain structures of T-A star PCL, T-A star PCL-Br, and T-A star PCL-b-P tBuA were confirmed by 1H NMR spectra. The amphiphilic T-A star PCL3-b-PAA3 has a CMC value of 2.57 × 10−6 g mL−1 and can form ribbon-like aggregates with a width of 200 nm–1 μm in THF/water after removal of THF by dialysis.

    10. Novel thermoresponsive fluorinated double-hydrophilic poly{[N-(2,2-difluoroethyl)acrylamide]-b-[N-(2-fluoroethyl)acrylamide]} block copolymers (pages 1976–1982)

      Jae Min Bak and Hyung-il Lee

      Article first published online: 19 FEB 2013 | DOI: 10.1002/pola.26578

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      Novel thermoresponsive double-hydrophilic fluorinated block copolymers, poly{[N-(2,2-difluoroethyl)acrylamide]-b-[N-(2-fluoroethyl)acrylamide]} (P2F-b-P1F), were successfully synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. Mono-fluorine substituted poly[N-(2-fluoroethyl)acrylamide] (P1F) is water-soluble while di-fluorine substituted poly[N-(2,2-difluoroethyl)acrylamide] (P2F) exhibits an LCST in water around 26–28 °C. Temperature-induced formation and disruption of nanoaggregates were achieved by virtue of the thermoresponsive nature of the P2F block. Temperature-triggered release of a model hydrophobic drug, coumarin 102, was also demonstrated.

    11. Efficient synthesis of monodisperse, highly crosslinked, and “living” functional polymer microspheres by the ambient temperature iniferter-induced “living” radical precipitation polymerization (pages 1983–1998)

      Man Zhao, Hongtao Zhang, Fengning Ma, Ying Zhang, Xianzhi Guo and Huiqi Zhang

      Article first published online: 12 FEB 2013 | DOI: 10.1002/pola.26579

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      The facile and efficient one-pot synthesis of monodisperse, highly crosslinked, and “living” functional copolymer microspheres by the ambient temperature iniferter-induced “living” radical precipitation polymerization (ILRPP) is described for the first time. Uniform poly(4-VP-co-EGDMA) microspheres (Dn = 0.28–1.44 μm) were readily obtained under different polymerization conditions. The general applicability of the ambient temperature ILRPP and the “livingness” of the resulting polymer microspheres were confirmed. Moreover, a “grafting from” particle growth mechanism was proposed for ILRPP.

    12. Tuning the frontier molecular orbital energy levels of n-type conjugated copolymers by using angular-shaped naphthalene tetracarboxylic diimides, and their use in all-polymer solar cells with high open-circuit voltages (pages 1999–2005)

      Shan-Ci Chen, Qingdong Zheng, Qikai Zhang, Dongdong Cai, Jinyun Wang, Zhigang Yin and Changquan Tang

      Article first published online: 7 FEB 2013 | DOI: 10.1002/pola.26580

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      Three new n-type copolymers with relative high-lying LUMO energy levels were synthesized by using an angular-shaped naphthalene diimide (NDI) as the building block and used in all-polymer solar cells that show a high Voc. The high Voc of 0.94 V is higher than that of solar cells based on linear-shaped NDI containing polymers (< 0.6 V).

    13. A Homotelechelic bis-terpyridine macroligand: One-step synthesis and its metallo-supramolecular self-assembly (pages 2006–2015)

      Ulrich Mansfeld, Andreas Winter, Martin D. Hager, Wolfgang Günther, Esra Altuntaş and Ulrich S. Schubert

      Article first published online: 14 FEB 2013 | DOI: 10.1002/pola.26586

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      A homodifunctional initiator was designed and applied for the controlled nitroxide-mediated polymerization of styrene to yield a α,ω-homotelechelic macroligand featuring two terpyridine moieties as designated metal binding sites. The self-assembly with FeII ions into a chain-extended metallopolymer and the disassembly thereof in the presence of a strong competitive ligand was investigated by UV–vis absorption spectroscopy and diffusion-ordered NMR spectroscopy.

    14. Synthesis and thermal properties of a bio-based polybenzoxazine with curing promoter (pages 2016–2023)

      CaiFei Wang, ChunHua Zhao, JiaQin Sun, SanQing Huang, XiangDong Liu and Takeshi Endo

      Article first published online: 19 FEB 2013 | DOI: 10.1002/pola.26587

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      A fully bio-based benzoxazine monomer has been synthesized from guaiacol, furfurylamine, and paraformaldehyde. Its polymerization behaviors, including the ring-opening polymerization temperature, the gel point time, and the char yield of the cured resin, were significantly improved by using methyl p-toluenesulfonate as promoter.

    15. Origins of the solvent effect on the propagation kinetics of acrylic acid and methacrylic acid (pages 2024–2034)

      Isa. Degirmenci, Tugba Furuncuoglu Ozaltın, Ozlem Karahan, Veronique Van Speybroeck, Michel. Waroquier and Viktorya Aviyente

      Article first published online: 20 FEB 2013 | DOI: 10.1002/pola.26589

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      Experimentally, the rate acceleration of PAA in water is found to be almost seven times faster than it is in bulk. In this study, DFT calculations together with MD simulations have been used to show that free radical polymerization in water is an entropically driven process.

    16. Synthesis of networked polymers by crosslinking reactions of polybenzoxazine bearing allyl group in the side chain (pages 2035–2039)

      Hiroaki Oie, Atsushi Sudo and Takeshi Endo

      Article first published online: 14 FEB 2013 | DOI: 10.1002/pola.26590

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      Networked poly(benzoxazine)s were synthesized from a linear polybenzoxazine bearing allyl side chains by two processes: (1) thermally induced oligomerization of the allyl side chains that were facilitated by addition of a radical source and (2) radically induced addition of thiols to the allyl side chains.

    17. Increased rubber content in high impact polypropylene via a sirius ziegler-natta catalyst containing nanoparticles (pages 2040–2048)

      Torvald Vestberg, Peter Denifl and Carl-Eric Wilén

      Article first published online: 14 FEB 2013 | DOI: 10.1002/pola.26592

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      A Ziegler–Natta catalyst containing SiO2 nanoparticles, average size 80 nm, was prepared with the Sirius emulsion-based catalyst preparation technology and used for producing high impact polypropylene. The nanoparticles increased the internal porosity of the homo PP matrix and via this allowed an almost doubled increase in rubber content before phasing stickiness compared to the catalyst without nanoparticles.

    18. Tandem dynamic kinetic resolution and enzymatic polycondensation to synthesize mPEG-functionalized poly(amine-co-ester)-type chiral prodrugs (pages 2049–2057)

      Xueqi Qian, Zhengyang Jiang, Xianfu Lin and Qi Wu

      Article first published online: 14 FEB 2013 | DOI: 10.1002/pola.26594

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      An efficient protocol to prepare amphiphilic poly(amine-co-ester) containing (R)-mexiletine with 99% ee by combining Candida antarctica lipase B/(Pd/C)-catalyzed dynamic kinetic resolution and subsequent polycondensation was developed. The copolymers can readily self-assemble into nanometer-scale-sized micelles with well-dispersed spheres, and their size distribution can be efficiently adjusted by changing the polymer concentration.

    19. Chain transfer agents in cationic photopolymerization of a bis-cycloaliphatic epoxide monomer: Kinetic and physical property effects (pages 2058–2067)

      Brian Dillman and Julie L. P. Jessop

      Article first published online: 19 FEB 2013 | DOI: 10.1002/pola.26595

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      A systematic study of kinetic and physical property modulation of cationically cured epoxy resins through incorporation of organic alcohols is presented. A variety of alcohols, which are chain transfer agents when incorporated into epoxy resins, have been studied. The molecular weight, functionality, steric hindrance, and relative nucleophilicity of the alcohol were shown to have profound effects on the curing of the resin and the ultimate properties realized as a crosslinked polymer.

    20. Structural optimization of highly branched thermally responsive polymers as a means of controlling transition temperature (pages 2068–2078)

      Kai Chang, Nathan C. Rubright, Patti D. Lowery and Lakeshia J. Taite

      Article first published online: 14 FEB 2013 | DOI: 10.1002/pola.26596

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      Highly branched poly(N-isopropylacrylamide) exhibits contrary behaviors to thermal transition temperature compared to linear analogs. These behaviors, such as the extremely low efficacy of end-group modification despite the high number of end groups present on a highly branched molecule lend insight into the pNIPAAm transition and behavior as a branched molecule. Sensitivities of these molecules to various forms of modification are also examined to determine suitability in engineering applications.

    21. Spotlight Article

      Organic–inorganic hybrid diblock copolymer composed of poly (ε-caprolactone) and poly(MA POSS): Synthesis and its nanocomposites with epoxy resin (pages 2079–2090)

      Lei Wang, Jingang Li, Lei Li and Sixun Zheng

      Article first published online: 14 FEB 2013 | DOI: 10.1002/pola.26597

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      The synthesis of organic-inorganic hybrid diblock copolymers composed of poly(ε-caprolactone) and poly(MA POSS) [PCL-b-P(MA POSS)] via reversible addition-fragmentation chain transfer polymerization of 3-methacryloxypropylheptaphenyl polyhedral oligomeric silsesquioxane with dithiobenzoate-terminated poly(ε-caprolactone) as the macromolecular chain transfer agent is reported. The organic–inorganic diblock copolymer was incorporated into epoxy and the organic–inorganic nanocomposites were successfully obtained.

    22. A facile strategy for synthesis of α,α′-heterobifunctionalized poly (ε-caprolactones) and poly (methyl methacrylate)s containing “clickable” aldehyde and allyloxy functional groups using initiator approach (pages 2091–2103)

      Prakash S. Sane, Bhausaheb V. Tawade, Indravadan Parmar, Savita Kumari, Samadhan Nagane and Prakash P. Wadgaonkar

      Article first published online: 14 FEB 2013 | DOI: 10.1002/pola.26598

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      The first-example of synthesis of α-aldehyde, α′-allyloxy heterobifunctionalized poly(ε-caprolactones), and poly(methyl methacrylate)s is reported employing appropriately substituted ROP and ATRP initators derived from commercially available 4,4′-bis(4-hydroxyphenyl) pentanoic acid. The usefulness of “clickable” heterobifunctionality on polymers is demonstrated by carrying out double metal-free click reactions such as aldehyde-aminoxy and thiol-ene reactions. Polymers possessing clickable α,α′-heterobifunctional groups represent a valuable precursor for synthesis of Y-shaped miktoarm and star copolymers.

  4. Notes

    1. Top of page
    2. Cover Image
    3. Rapid Communication
    4. Articles
    5. Notes
    1. RAFT miniemulsion polymerization using dioctyl sodium sulfosuccinate (pages 2104–2109)

      Siming Dong, Siqing Cheng and Per B. Zetterlund

      Article first published online: 14 FEB 2013 | DOI: 10.1002/pola.26591

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      The anionic surfactant dioctyl sodium sulfosuccinate (AOT) has been shown to operate well as a surfactant in aqueous miniemulsion polymerization of styrene both for conventional radical polymerization and RAFT polymerization. AOT is generally more soluble in hydrophobic monomers than in water, and is as such rather unique for an aqueous miniemulsion system. The particle size obtained was smaller than what is customary for both conventional radical polymerization and RAFT polymerization in miniemulsion.

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