Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 51 Issue 18

15 September 2013

Volume 51, Issue 18

Pages i–iv, 3769–3984

  1. Cover Image

    1. Top of page
    2. Cover Image
    3. Highlight
    4. Articles
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      Cover Image, Volume 51, Issue 18 (pages i–ii)

      Version of Record online: 5 AUG 2013 | DOI: 10.1002/pola.26876

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      An ornithine-based poly(ester amide) (above left) degrades more rapidly than a lysine-based PEA (below right) because it is capable of intramolecular cyclization (yellow scissors) upon light-triggered deprotection, in addition to hydrolysis (blue scissors). Nanoparticles formulated from the ornithine-based PEA thus disassemble rapidly, releasing cargo. By quantifying the amount of cyclization and ester hydrolysis, Caroline de Gracia Lux, Jason Olejniczak, Nadezda Fomina, Mathieu L. Viger, and Adah Almutairi demonstrate on page 3783 that only the polymer capable of forming a 6-membered ring cyclizes. This work introduces intramolecular cyclization as an efficient mechanism that can be incorporated into other polymeric materials for on-demand degradation.

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      Inside Cover, Volume 51, Issue 18 (pages iii–iv)

      Version of Record online: 5 AUG 2013 | DOI: 10.1002/pola.26877

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      Peroxybromination is an environment friendly process that is carried out without using elemental bromine. In the process bromine is generated in situ from NaBr by H2O2. No HBr elimination takes place in the reaction, so that one bromine atom is consumed per brominated site. Application of peroxybromination to poly(vinyl methyl ketone) (PVMK) selectively brominates methyne carbon. The use of brominated PVMK as multifunctional ATRP initiator in polymerization with MMA or styrene yields bottle brush polymers, the continued reaction of which results in self-crosslinking. Moreover active ATRP initiation sites generated on styrene-DVB-VMK terpolymer beads allows creation of polymer brushes on the surfaces.

  2. Highlight

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    2. Cover Image
    3. Highlight
    4. Articles
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      The emerging utility of ketenes in polymer chemistry (pages 3769–3782)

      Frank A. Leibfarth and Craig J. Hawker

      Version of Record online: 25 JUN 2013 | DOI: 10.1002/pola.26797

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      This Highlight focuses on the modern renaissance of ketenes in polymer science. For almost a century ketenes, which were first discovered by Hermann Staudinger in 1905, have been an underexplored functional group in polymer chemistry. The recent revival of ketenes has been driven by the discovery of modular, stable, and user friendly methods to access this versatile functional groups in polymer systems, leading to powerful platform technologies for the production of next-generation materials.

  3. Articles

    1. Top of page
    2. Cover Image
    3. Highlight
    4. Articles
    1. Intramolecular cyclization assistance for fast degradation of ornithine-based poly(ester amide)s (pages 3783–3790)

      Caroline de Gracia Lux, Jason Olejniczak, Nadezda Fomina, Mathieu L. Viger and Adah Almutairi

      Version of Record online: 11 JUN 2013 | DOI: 10.1002/pola.26788

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      Inspired by the hydrolysis-independent, spontaneous cyclization of ornithine in peptides, poly(ester amide)s containing protected ornithine (PEA-Orn) side chains along the backbone were synthesized. PEA-Orn degrades upon deprotection through intramolecular cyclizations over 40 times faster than PEA-Lys, a control polymer uncapable of cyclization that degrades only by ester hydrolysis. PEA-Orn-formulated particles encapsulating iron oxide nanoparticles completely degrade and release payload as a result of both polymer degradation and a decrease in hydrophobicity caused by the deprotection of amines.

    2. Hollow mesoporous silica nanoparticles modified with coumarin-containing copolymer for photo-modulated loading and releasing guest molecule (pages 3791–3799)

      Jing Yang, Wei-Dong He, Chen He, Jing Tao, Sheng-Qi Chen, Shao-Min Niu and Shao-Lin Zhu

      Version of Record online: 20 JUN 2013 | DOI: 10.1002/pola.26793

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      Hollow mesoporous silica nanoparticles grafted with a photo-responsive copolymer of P(MMA-co-CMA) were used as the smart nanocarrier for guest molecules. The amount of pyrene loaded in nanoparticles reached as high as 5.1 g for 1 g of nanoparticles. P(MMA-co-CMA) grafting chains acted as photo-gatekeepers for loading and releasing pyrene.

    3. Multiblock copolymers of ε–caprolactone and ethylene glycol containing periodic side-chain carboxyl groups: Synthesis, characterization, and nanoparticle preparation (pages 3800–3809)

      Anna Maria Lapi, Angelina Altomare, Michele Alderighi, Andrea Corti, Alberto Dessy, Federica Chiellini, Antonella Solimando and Roberto Solaro

      Version of Record online: 22 JUN 2013 | DOI: 10.1002/pola.26795

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      Multiblock copolymers containing periodically spaced side-chain carboxyl groups are readily obtained by a two-step synthesis involving the preparation of poly(ε-caprolactone)–poly(ethylene glycol)–poly(ε-caprolactone) triblock copolymers followed by chain extension with pyromellitic dianhydride. The synthesized carboxylated polymers can be easily processed into protein-loaded nanoparticle suspensions.

    4. Synthesis of poly(3-hexylthiophene)-block-poly(ethylene)-block-poly(3-hexylthiophene) via a combination of ring-opening olefin metathesis polymerization and grignard metathesis polymerization (pages 3810–3817)

      Songsu Kang, Robert J. Ono and Christopher W. Bielawski

      Version of Record online: 22 JUN 2013 | DOI: 10.1002/pola.26798

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      Poly(3-hexylthiophene)-block-poly(butadiene)-block-poly(3-hexylthiophene triblock) copolymers were synthesized using ring-opening metathesis polymerization and Grignard metathesis polymerization. The chain length of each block was tuned by varying the respective initial monomer/chain transfer agent or monomer/macroinitiator ratios. Hydrogenation of the aforementioned triblock copolymer afforded a new rod–coil–rod copolymer, poly(3-hexylthiophene)-b-poly(ethylene)-b-poly(3-hexylthiophene), that was found to undergo phase separation in the solid state.

    5. Imide-functionalized naphthodithiophene based donor-acceptor conjugated polymers for solar cells (pages 3818–3828)

      Tanmoy Dutta, Yong Li, Aaron L. Thornton, Da-Ming Zhu and Zhonghua Peng

      Version of Record online: 22 JUN 2013 | DOI: 10.1002/pola.26799

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      Four donor-acceptor alternating conjugated copolymers based on a new imide-functionalized naphtho[1,2-b:3,4-d′]dithiophene monomer and 2,2'-bithiophene comonomers have been synthesized and characterized. Varying the substituents at the 3,3' positions of the comonomer unit has a profound effect on the conformational twist of the backbone, and consequently the optical, redox, and photovoltaic properties of the copolymers. Bulk heterojunction solar cells of these copolymers blended with [6,6]-phenyl-C71-butyric acid methyl ester show power conversion efficiencies up to 2.45%.

    6. Controlled synthesis of new amphiphilic glycopolymers with liquid crystal grafts (pages 3829–3839)

      Khalid Ferji, Cécile Nouvel, Jérôme Babin, Pierre-Antoine Albouy, Min-Hui Li and Jean-Luc Six

      Version of Record online: 28 JUN 2013 | DOI: 10.1002/pola.26804

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      Controlled ATRP of diethylene glycol cholesteryl ether acrylate (DEGCholA) was shown. Then, graft glycopolymers containing polysaccharidic backbone and cholesterol-based liquid crystal polymeric grafts were produced by initiating the ATRP of DEGCholA from a dextran-based macroinitiator. The study of mesomorphic properties of PDEGCholA chains and graft glycopolymer revealed that both of them exhibit an interdigitated smectic A phase and the same clearing temperature. This study paves the way toward the preparation of liquid crystal glycopolymers.

    7. Air-stable copper derivatives as efficient catalysts for controlled lactide polymerization: Facile synthesis and characterization of well-defined benzotriazole phenoxide copper complexes (pages 3840–3849)

      Chen-Yu Li, Shi-Jie Hsu, Chin-lung Lin, Chen-Yen Tsai, Jun-Han Wang, Bao-Tsan Ko, Chia-Her Lin and Hsi-Ya Huang

      Version of Record online: 12 JUN 2013 | DOI: 10.1002/pola.26780

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      This study reports controlled catalysis for lactide (LA) polymerizations catalyzed by air-stable Cu complexes bearing benzotriazole phenoxide ligands in the presence of various alcohol initiators. The controlled character of complex 3 enables preparation of two-arm linear, three-arm star-shaped PLLAs, and PEG-b-PLLA copolymer.

    8. A study of the effects of thiols on the frontal polymerization and pot life of multifunctional acrylate systems with cumene hydroperoxide (pages 3850–3855)

      Alejandra Morales and John A. Pojman

      Version of Record online: 7 JUN 2013 | DOI: 10.1002/pola.26782

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      The front velocity of the frontal polymerization of trimethylol propane triacrylate as a function of two different thiols with cumene hydroperoxide as the initiator is presented. Unlike with peroxide initiators, the velocity increases with thiol concentration.

    9. Radical copolymerization of acrylonitrile with 2,2,2-trifluoroethyl acrylate for dielectric materials: Structure and characterization (pages 3856–3866)

      Salima Atlas, Mustapha Raihane, Anders Hult, Michael Malkoch, Mohammed Lahcini and Bruno Ameduri

      Version of Record online: 11 JUN 2013 | DOI: 10.1002/pola.26783

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      A novel copolymer based on acrylonitrile (AN) and 2,2,2-trifluoroethyl acrylate (ATRIF) was synthesized by free radical process. Its composition and microstructure were studied by NMR analysis and reactivity ratios, showing a statistical structure. Preliminary investigations on the thermal properties of poly(AN-co-ATRIF) copolymers showed comparatively high glass transition temperature and thermal stability with respect to those of poly(ATRIF) homopolymer. These features are primary requirements for potential applications as dielectric materials.

    10. Polyaddition of bifunctional 1,3-benzoxazine and 2-methylresorcinol (pages 3867–3872)

      Hiroaki Oie, Atsushi Mori, Atsushi Sudo and Takeshi Endo

      Version of Record online: 7 JUN 2013 | DOI: 10.1002/pola.26784

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      A highly efficient polyaddition system consisting of bifunctional benzoxazines and 2-methylresorcinol that proceeds at ambient temperature has been developed. The resulting linear polymers bearing phenolic and tertiary amino groups in the main chain exhibited high glass transition temperatures, which were comparable to those of the linear polybenzoxazines synthesized by the conventional ring-opening polymerization of monofunctional benzoxazines.

    11. Photoinduced depolymerization of poly(olefin sulfone)s possessing photobase generator side-chains: Effect of spacer-chain length (pages 3873–3880)

      Takeo Sasaki, Takumi Yoneyama, Shota Hashimoto, Sumie Takemura and Yumiko Naka

      Version of Record online: 11 JUN 2013 | DOI: 10.1002/pola.26787

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      Photoinduced depolymerization of poly(olefin sulfone)s possessing photobase generators in the side-chain was investigated. Irradiation with UV light generated base on the side-chains and induced depolymerization based on proton abstraction on the main-chain. The effect of the length of the spacer chain, which connects the photobase-generating moiety to the polymer main chain on the photoinduced depolymerization, also was investigated.

    12. Enzymatic syntheses of unsaturated polyesters based on isosorbide and isomannide (pages 3881–3891)

      Alliny F. Naves, Henrique T. C. Fernandes, Ana P. S. Immich and Luiz H. Catalani

      Version of Record online: 11 JUN 2013 | DOI: 10.1002/pola.26789

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      The enzymatic copolymerization of isosorbide or isomannide with diethyl adipate and fractions of different unsaturated diesters was examined using CAL-B as catalyst in a one-step process. Syntheses with linear diols were carried out in bulk to evaluate the reactivity of cyclic diols in producing unsaturated polyesters using enzymatic catalysis and to evaluate the occurrence of addition side reactions on the double bonds.

    13. Regio-selective peroxybromination of poly(vinyl methyl ketone) as versatile tool for generation active ATRP initiation sites on solid surfaces (pages 3892–3900)

      Baris Kumru, Baris Gure and Niyazi Bicak

      Version of Record online: 13 JUN 2013 | DOI: 10.1002/pola.26790

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      Peroxybromination of poly(vinylmethyl ketone) in aqueous dispersion results in selective bromination at the methyne carbon, from which atom transfer radical polymerization (ATRP) of MMA and styrene can be initiated to give bottle brush polymers. Moreover, peroxybromination of PVMK segments incorporated into PS-DVB beads provide an easy access to active ATRP initiation sites on the solid surfaces.

    14. Spray-processable thiazolothiazole-based copolymers with altered donor groups and their electrochromic properties (pages 3901–3906)

      Hava Zekiye Akpinar, Yasemin Arslan Udum and Levent Toppare

      Version of Record online: 13 JUN 2013 | DOI: 10.1002/pola.26791

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      Electrochromic properties of thiazolothiazole containing copolymers functionalized with thiophene and furan bridges were investigated. Both copolymers are solution processable and revealed multichromic properties with applied small potential differences.

    15. Fast and effective copper(0)-mediated simultaneous chain- and step-growth radical polymerization at ambient temperature (pages 3907–3916)

      Xiaomin Zhang, Heqin Dou, Zhengbiao Zhang, Wei Zhang, Xiulin Zhu and Jian Zhu

      Version of Record online: 13 JUN 2013 | DOI: 10.1002/pola.26792

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      Vinyl-conjugated monomer (methyl acrylate, MA) and allyl 2-bromopropanoate (ABP)-possessing unconjugated C[DOUBLE BOND]C and active C[BOND]Br bonds were polymerized via the Cu(0)-mediated simultaneous chain- and step-growth radical polymerization at ambient temperature using Cu(0) as catalyst, N,N,N′,N″,N″-pentamethyldiethylenetriamine as ligand, and dimethyl sulfoxide as solvent. The conversion reached higher than 98% within 20 h. The obtained polymers showed block structure consisting of polyester and vinyl polymer moieties.

    16. Biodegradable and thermosensitive micelles of amphiphilic polyaspartamide derivatives containing aromatic groups for drug delivery (pages 3917–3924)

      Yingying Ma, Xulin Jiang and Renxi Zhuo

      Version of Record online: 20 JUN 2013 | DOI: 10.1002/pola.26794

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      Facile fabrication of paclictaxel-loaded polymeric micelles based on new thermosensitive and degradable amphiphilic polyaspartamide derivatives with aromatic structures by an easy and quick heating method without using toxic organic solvent is reported. The obtained drug-loaded micelles with excellent drug-loading efficiency (>90%) and capacity (up to 29%) show sustained drug release and obvious anticancer activity, whereas blank micelles are nontoxic.

    17. Facile synthesis of pH-responsive glycopolypeptides with adjustable sugar density (pages 3925–3931)

      Robert Mildner and Henning Menzel

      Version of Record online: 20 JUN 2013 | DOI: 10.1002/pola.26796

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      The synthesis of glycopolypeptides from a poly(α,l-glutamic acid) (PGA) precursor via a polymer-analogous aqueous amide coupling approach allows an easy adjustment of the sugar density and with that fine-tuning of the properties. PGAs functionalized with the model sugar d-glucosamine exhibit a pH-responsive helix-coil transition and biological activity depending on the sugar density.

    18. Octahydrogenated retinoic acid-conjugated glycol chitosan nanoparticles as a novel carrier of azadirachtin: Synthesis, characterization, and in vitro evaluation (pages 3932–3940)

      Wei Lu, Meng-Ling Lu, Qing-Peng Zhang, Yong-Qing Tian, Zhi-Xiang Zhang and Han-Hong Xu

      Version of Record online: 26 JUN 2013 | DOI: 10.1002/pola.26801

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      As a potential “green” nanocarrier of pesticides, novel amphiphilic self-assembled octahydrogenated retinoic acid-glycol chitosan (OR-GC) nanoparticles have been synthesized and characterized, which can effectively load the poorly water-soluble pesticide AZA (about 74%). Compared with free AZA in organic solvents, the AZA-OR-GC nanoparticles showed favorable inhibition of cell proliferation and sustained drug release performance in Sl-1 cells in vitro.

    19. Synthesis of polydopamine-coated graphene–polymer nanocomposites via RAFT polymerization (pages 3941–3949)

      Renpeng Gu, William Z. Xu and Paul A. Charpentier

      Version of Record online: 26 JUN 2013 | DOI: 10.1002/pola.26802

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      Polydopamine-coated graphene was synthesized by means of oxidative exfoliation of graphite followed by reduction of the graphene oxide sheets via self-polymerization of dopamine. A reversible addition fragmentation chain transfer (RAFT) agent containing a carboxyl group was then chemically bonded to the surface of the polydopamine-coated graphene via an esterification reaction to afford a macro-RAFT agent. Graphene–polymer nanocomposites were synthesized by RAFT polymerization of three different vinyl monomers including methyl methacrylate, N-isopropylacrylamide, and tert-butyl acrylate, by using the macro-RAFT agent, with the graphene–poly(N-isopropylacrylamide) nanocomposite showing thermoresponsive behavior.

    20. Synthesis of transparent and thermally stable polycyanurates and their thermal rearrangement (pages 3950–3955)

      Yoshitaka Saito, Hidetoshi Matsumoto, Tomoya Higashihara and Mitsuru Ueda

      Version of Record online: 22 JUN 2013 | DOI: 10.1002/pola.26803

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      Transparent and themally stable polycyanurates have been successfully prepared by the phase-transfer-catalyzed polycondensation of 2,4-dichloro-6-methoxy-1,3,5-triazine with bisphenol monomers in the presence of quaternary ammonium salts. The solubility of polymer films containing 1 wt % of tetrabutylammonium bromide can be changed by thermal rearrangement. The partially rearranged films keep high transparency and low birefringence. Polycyanurates are one of the candidates for functional transparent films, which are required for the multilayer coating process and environmental stabilities.

    21. Synthesis of high-performance polyurethanes with rigid 5-6-5-fused ring system in the main chain from naturally occurring myo-inositol (pages 3956–3963)

      Atsushi Sudo, Yoshiya Shibata and Ayano Miyamoto

      Version of Record online: 22 JUN 2013 | DOI: 10.1002/pola.26805

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      myo-Inositol was transformed into the corresponding diol bearing two cyclic ketals. The polyaddition of the diol with diisocyanate gave the corresponding polyurethanes with a 5-6-5-fused ring system in the repeating unit of which rigidity contributed to the enhanced heat resistance of the polyurethanes.

    22. Synthesis of novel hyperbranched polymers featuring oxazoline linear units and their application in fast-drying solvent-borne coating formulations (pages 3964–3974)

      Ge Cheng, Barnaby W. Greenland, Chris Lampard, Neal Williams, Malkit S. Bahra and Wayne Hayes

      Version of Record online: 26 JUN 2013 | DOI: 10.1002/pola.26807

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      Novel acid-terminated hyperbranched polymers containing adipic acid and oxazoline monomers derived from oleic and linoleic acid have been synthesized via a bulk polymerization procedure. Branching was achieved as a consequence of an acid-catalyzed opening of the oxazoline rings. These polymers, when formulated with commercially available alkyd resins, cure rapidly to afford tough coatings when compared to industrial standard formulations.

    23. Copoly(p-phenylene) containing azacrown ether: Synthesis, optical properties, and application for chemical sensor (pages 3975–3984)

      Chia-Shing Wu, Chiao-Pei Chen and Yun Chen

      Version of Record online: 28 JUN 2013 | DOI: 10.1002/pola.26811

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      Copoly(p-phenylene) (P1) containing pendent azacrown ether and ethylene glycol ether was prepared and applied for a chemical sensor. P1 exhibited specific selectivity and high sensitivity toward Zn2+, with the Stern–Volmer coefficient (Ksv) being 3.66 ×106 M−1. P1 maintained high selectivity toward Zn2+ in the presence of fifteen interfering metal cations.