Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 48 Issue 11

1 June 2010

Volume 48, Issue 11

Pages 2257–2516

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      Polyvinylamine at last (pages 2257–2283)

      Robert K. Pinschmidt Jr

      Version of Record online: 26 APR 2010 | DOI: 10.1002/pola.23992

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      A 40+ year quest finally resulted, in 2002, in the commercialization of N-vinylformamide, a simple, economically practical, and free radically polymerizable monomer efficiently convertible to the full range of atom-economic vinylamine polymers, copolymers, and derivatives.

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    1. Controllable preparation of epoxy-functionalized magnetic polymer latexes with different morphologies by modified miniemulsion polymerization (pages 2284–2293)

      Yawen Xu, Hong Xu and Hongchen Gu

      Version of Record online: 26 APR 2010 | DOI: 10.1002/pola.23984

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      We obtained the functional magnetic polymer latexes (MPLs) with epoxy groups introduced via a modified miniemulsion polymerization route. The epoxy group content on the surface could be controlled by seed emulsion polymerization followed. A novel approach to achieve manipulation of the morphology of the MPLs based on kinetic control of the polymerization system was also developed. MPLs with different morphologies were obtained ranging from core-shell microstructures, dispersed microstructures to asymmetric microstructure. The mechanisms of the contribution of kinetic factors to the formation of the different morphologies were further investigated.

    2. Hybrid atom transfer radical polymerization system for balanced polymerization rate and polymer molecular weight control (pages 2294–2301)

      Mark Machado, Santiago Faucher and Shiping Zhu

      Version of Record online: 26 APR 2010 | DOI: 10.1002/pola.23993

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      A hybrid polymerization system that combines the fast reaction kinetics of conventional free radical polymerization and the control of molecular weight and distribution afforded by ATRP has been investigated. Conversions greater than of 90% were achieved with ATRP catalyst concentrations of less than 20 ppm within 2 h for the hybrid ATRP system as compared to ATRPs where achieving such conversions would take up to 24 h. These reaction conditions lead to living and controlled polymerizations with polydispersities below 1.30. Chain extension experiments from a synthesized macroinitiator confirm the living characteristics of the hybrid ATRP process.

    3. Poly(methyl methacrylate) copolymers containing multiple, pendent plasticizing groups (pages 2302–2310)

      Huseyin Tas and Lon J. Mathias

      Version of Record online: 26 APR 2010 | DOI: 10.1002/pola.23994

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      New ether dimer (ED-Eh) and diester (EHDE) derivatives of α-(hydroxymethyl)acrylate, each having two 2-ethylhexyl side chains, and an amine-linked di(2-ethylhexyl)acrylate (AL-Eh), having three 2-ethylhexyl side chains, were synthesized and (co)polymerized under free radical conditions. Copolymerization of these monomers and 2-ethylhexyl methacrylate with methyl methacrylate (MMA) showed that the impacts of these monomers on depression of Tg's are identical. The magnitude of decrease in Tg's was quantitatively related to the number of the 2-ethylhexyl side groups in the copolymers rather than their placement on the same or randomly incorporated repeat units.

    4. Tuning the electronic properties of conjugated polymer by tethering low-bandgap rhenium(I) complex on the main chain (pages 2311–2319)

      Chris S. K. Mak, Qing Yun Leung, Chi Ho Li and Wai Kin Chan

      Version of Record online: 26 APR 2010 | DOI: 10.1002/pola.23996

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      Low-bandgap rhenium(I) complex possesses absorption onset in the near-infrared region was successfully tethered onto π-conjugated polymer with good solubility and film-forming properties. The photophysical and electrochemical properties of the metal-free polymer can be varied simply by metal coordination. This facial approach provides synthetic feasibility for coordinating wide range of metal ions on the pendant, and the resulting low bandgap polymer can be a potential candidate for light harvesting material in solar cell applications.

    5. Thermoresponsive brush copolymers with poly(propylene oxide-ran-ethylene oxide) side chains via metal-free anionic polymerization “grafting from” technique (pages 2320–2328)

      Junpeng Zhao, Guangzhao Zhang and Stergios Pispas

      Version of Record online: 26 APR 2010 | DOI: 10.1002/pola.23997

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      Well-defined brush copolymers with side chains being poly(propylene oxide-ran-ethylene oxide) were synthesized via metal-free anionic ring-opening polymerization, using poly(p-hydroxystyrene) as the backbone polymer and t-BuP4 as the polymerization promoter. The results from light scattering and fluorescence spectroscopy indicated that the brush copolymers underwent slight intramolecular chain contraction/association and much more profound intermolecular aggregation, followed by macrophase separation, by increasing solution temperature.

    6. New ethyl cellulose/acrylic hybrid latexes and coatings via miniemulsion polymerization (pages 2329–2339)

      R. Chen, F. Chu, C. Gauthier, L. Chazeau, I. Chaduc, E. Bourgeat-Lami and M. Lansalot

      Version of Record online: 26 APR 2010 | DOI: 10.1002/pola.23998

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      Ethyl cellulose (EC) was incorporated into film-forming poly(methyl methacrylate-co-butyl acrylate) (P(MMA-co-BA)) latexes via miniemulsion polymerization. The latexes elaborated in the presence of a hydrosoluble initiator showed limited colloidal stability attributed to phase incompatibility between EC and the acrylic polymer. Those stability issues were overcome by using triethylene glycol dimethacrylate (TEGDMA) as crosslinker and dilauroyl peroxide (LPO) as oil-soluble initiator, capable of undergoing graft chemical reaction with the EC backbone. The resulting hybrid films displayed enhanced thermo-mechanical properties compared with EC-free films or physical blends. This was tentatively interpreted by the formation of a percolating EC-based hybrid phase within the film.

    7. Poly(γ-benzyl-L-glutamate)-functionalized single-walled carbon nanotubes from surface-initiated ring-opening polymerizations of N-carboxylanhydride (pages 2340–2350)

      Haoyu Tang and Donghui Zhang

      Version of Record online: 26 APR 2010 | DOI: 10.1002/pola.24001

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      Single-walled carbon nanotubes (SWCNTs) have been functionalized with poly(γ-benzyl glutamate) (PBLG) by ring-opening polymerizations of γ-benzyl-L-glutamic acid-based N-carboxylanhydrides (NCA-BLG) using amino-functionalized SWCNTs (SWCNT-NH2) as initiators. The FTIR study reveals that surface-attached PBLGs adopt random-coil conformations in contrast to the physically absorbed or bulk PBLGs, which exhibit α-helical conformations. Microfibers containing SWCNT-PBLG and PBLG can be prepared via electrospinning. WAXS analysis reveals that SWCNTs are evenly distributed among PBLG rods in solution and in the solid state where PBLGs form a short-range nematic phase interspersed with amorphous domains.

    8. New thiophene-phenylene-thiophene acceptor random conjugated copolymers for optoelectronic applications (pages 2351–2360)

      Jung-Hsun Tsai, Chu-Chen Chueh, Wen-Chang Chen, Chao-Ying Yu, Gue-Wuu Hwang, Ching Ting, En-Chen Chen and Hsin-Fei Meng

      Version of Record online: 26 APR 2010 | DOI: 10.1002/pola.24002

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      New low band gap thiophene-phenylene-thiophene (TPT)-based donor-acceptor-donor random copolymers were synthesized for optoelectronic device applications. The optical band gaps and FET hole mobilities of the three prepared copolymers were in the range of 1.48–1.74 eV and 2.2–4.7 × 10–3 cm2 V–1 s–1, respectively. The power conversion efficiency of the polymer photovoltaic cells could be as high as 3.71%. Besides, the near-infrared photodetector device prepared from PTPTDTQ0.26DPP0.34 showed a high external quantum efficiency exceeding 32% at 700 nm (under −3 V bias) and fast-speed response.

    9. Polyisobutylene-based polyurethanes. VI. Unprecedented combination of mechanical properties and oxidative/hydrolytic stability by H-bond acceptor chain extenders (pages 2361–2371)

      Gabor Erdodi, Jungmee Kang and Joseph P. Kennedy

      Version of Record online: 26 APR 2010 | DOI: 10.1002/pola.24003

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      We describe the design, synthesis, characterization, and testing of novel polyurethanes (PUs) exhibiting unprecedented combinations of outstanding mechanical properties and oxidative/hydrolytic stabilities. This achievement is due to the use of polyisobutylene (PIB) soft segments plus flexible H-bond acceptor chain extenders (HACEs). PUs containing 60–70% PIB and HACE showed excellent mechanical properties and oxidative/hydrolytic stability on exposure to nitric acid, whereas Carbothane®, Bionate®, and Elast-Eon™ severely degraded under the same conditions. The novel PUs are promising candidates for biomaterials and industrial applications where a combination of mechanical properties and oxidative/hydrolytic stability is of the essence.

    10. Salt-induced microphase separation of amorphous dendritic poly(ethylene oxide)-block-linear polystyrene copolymers (pages 2372–2376)

      Byoung-Ki Cho, Seung-Hyun Kim and Eunji Lee

      Version of Record online: 26 APR 2010 | DOI: 10.1002/pola.24005

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      Dendritic poly(ethylene oxide)-block-linear polystyrene copolymer shows an induced lamellar morphology by salt addition. The lamellar thickness drastically reduces at the PS glass transition temperature, so as to alleviate the conformational energy of the flexible linear polystyrene.

    11. Synthesis and characterization of stimuli-responsive porous/hollow nanoparticles by self-assembly of chitosan-based graft copolymers and application in drug release (pages 2377–2387)

      Chung-Yang Chuang, Trong-Ming Don and Wen-Yen Chiu

      Version of Record online: 26 APR 2010 | DOI: 10.1002/pola.24006

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      In this work, stimuli-responsive porous/hollow nanoparticles were prepared by self- assembly of chitosan-based graft copolymers. The particle size and morphology of nanoparticles varied with the pH value or temperature of the medium.

    12. Photopolymerization of poly(ethylene glycol) dimethacrylates: The influence of ionic liquids on the formulation and the properties of the resultant polymer materials (pages 2388–2409)

      Sergey A. Chesnokov, Marya Yu. Zakharina, Alexander S. Shaplov, Elena I. Lozinskaya, Inna A. Malyshkina, Gleb A. Abakumov, Frederic Vidal and Yakov S. Vygodskii

      Version of Record online: 26 APR 2010 | DOI: 10.1002/pola.24008

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      Photopolymerization of a set of poly(ethylene glycol)dimethacrylates [PEGDM(n)] in the presence of various ionic liquids (ILs) was investigated. It was found that the influence of ILs nature upon the photopolymerization kinetics of dimethacrylates is rather complicated. For the explanation of this, the conception depicting in liquid monomers, the presence of stable intermolecular structures with kinetically favorable or unfavorable molecules arrangement was suggested. The destruction of the monomer associates by ILs leads mainly to the acceleration of its polymerization. It was further revealed that ILs strongly influence the properties of obtained polymer materials, namely the thermal stability, ionic conductivity, Tg, etc.

    13. Bioinspired polymer functionalized with a diiron carbonyl model complex and its assembly onto the surface of a gold electrode via “click” chemistry (pages 2410–2417)

      Xiang Ru, Xianghua Zeng, Zhimei Li, David J. Evans, Caixia Zhan, Ying Tang, Lianjie Wang and Xiaoming Liu

      Version of Record online: 26 APR 2010 | DOI: 10.1002/pola.24010

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      The {Fe2(CO)6} core, related to the diiron subunit of [FeFe]-hydrogenase, embedded into polyene-based materials via polymerization. An electrode was assembled via chemically anchoring the functionalized polymer onto the surface of a gold electrode through “click” chemistry, which was premodified with an alkyl thiol pendant with a terminal azido group. Electron transfer from the gold matrix to the immobilized polymer was observed.

    14. Photoreactive nanomatrix structure formed by graft-copolymerization of 1,9-nonandiol dimethacrylate onto natural rubber (pages 2418–2424)

      Yoshimasa Yamamoto, Patjaree Suksawad, Nanthaporn Pukkate, Tatsuya Horimai, Osamu Wakisaka and Seiichi Kawahara

      Version of Record online: 26 APR 2010 | DOI: 10.1002/pola.24011

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      Formation of photoreactive nanomatrix structure was investigated by graft-copolymerization of an inclusion complex of 1,9-nonandiol dimethacrylate (NDMA) with β-cyclodextrin onto natural rubber particle using an initiator. The graft copolymer was characterized by 1H NMR and FTIR after coagulation. The morphology of the film specimen, prepared from the graft copolymer, was observed by transmission electron microscopy after staining the film with OsO4. Natural rubber particle of about 1.0 μm in diameter was dispersed in poly(NDMA) matrix of about 10nm in thickness.

    15. One-pot synthesis of well-defined multiblock polymer: Combination of ATRP and RAFT polymerization involving cyclic trithiocarbonate (pages 2425–2429)

      Yusong Wu and Qi Wang

      Version of Record online: 26 APR 2010 | DOI: 10.1002/pola.24012

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      Multiblock polymer was prepared by combination of ATRP (CuBr/tris[(2-pyridyl)methyl]amine/RX) and RAFT polymerization involving cyclic trithiocarbonate (CTTC). The average block number of polymer was controlled by concentration ratio of CTTC to alkyl halide, and the molecular weight of block was well regulated by concentration of CTTC and monomer conversion. During the polymerization, ATRP catalyst provided constant amount of radicals, which generated predictable number of polymer chains, and CTTC underwent ring-opening polymerization and the incorporated trithiocarbonate moiety derived from CTTC performed as RAFT agent, which produced the blocks with anticipated molecular weight and narrow molecular weight distribution.

    16. Facile, one-pot synthesis of aromatic diamine-based benzoxazines and their advantages over diamines as epoxy hardeners (pages 2430–2437)

      Sheng Lung Chang and Ching Hsuan Lin

      Version of Record online: 26 APR 2010 | DOI: 10.1002/pola.24013

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      Three aromatic diamine-based benzoxazines were successfully prepared by a facile, clean, one-pot procedure The resultant benzoxazines were applied as hardeners for cresol novolac epoxy (CNE). The processing window, the latent curing characteristic, and the miscibility of benzoxazine/CNE systems were discussed.

    17. Synthesis and solvent-dependent micellization of the amphiphilic block copolymer poly(styreneboronic acid)-block-polystyrene (pages 2438–2445)

      Chengzhong Cui, Edward M. Bonder, Yang Qin and Frieder Jäkle

      Version of Record online: 26 APR 2010 | DOI: 10.1002/pola.24014

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      The amphiphilic organoboron block copolymer poly(styreneboronic acid)-block-polystyrene forms different aggregated structures depending on pH and solvent conditions based on transmission electron microscopy studies.

    18. Structure-property relationships in densely grafted π-stacked polymers (pages 2446–2461)

      Andrea Cappelli, Marco Paolino, Paolo Anzini, Germano Giuliani, Salvatore Valenti, Marianna Aggravi, Alessandro Donati, Raniero Mendichi, Lucia Zetta, Antonella Caterina Boccia, Fabio Bertini, Filippo Samperi, Salvatore Battiato, Eugenio Paccagnini and Salvatore Vomero

      Version of Record online: 26 APR 2010 | DOI: 10.1002/pola.24016

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      Three methyl end-capped oligo(ethylene glycol) (MOEG) ethers (1b–d) and a methoxyderivative (1a) of a benzofulvene monomer were synthesized and induced to polymerize spontaneously to obtain soluble π-stacked densely grafted polymers (poly-1b–d) and model polymer poly-1a. The physicochemical features of the synthesized polymers were compared in a structure-property relationship study. The solubility of poly-1a–d depends on the number of the oligo(ethylene glycol) monomeric units. In particular, poly-1d, featuring a long MOEG side chain (n = 9), shows an amphiphilic character and is soluble in a number of organic solvents, whereas it interacts with water to give isolated macromolecules.

    19. Overcoming the oxygen inhibition in the photopolymerization of acrylates: A study of the beneficial effect of triphenylphosphine (pages 2462–2469)

      C. Belon, X. Allonas, C. Croutxé-barghorn and J. Lalevée

      Version of Record online: 26 APR 2010 | DOI: 10.1002/pola.24017

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      The efficiency of triphenylphosphine (TPP) used as peroxy radical scavenger in free radical photopolymerization is investigated through real time infrared spectroscopy and laser flash photolysis. The key factors involved in the process are pointed out and a mechanism is proposed to account for the beneficial effect of TPP.

    20. Solving the loss of orthogonality during the polyaddition of α-azide-ω-alkyne monomers catalyzed by Cu(PPh3)3Br: Application to the synthesis of high-molar mass polytriazoles (pages 2470–2476)

      Sandra Binauld, Etienne Fleury and Eric Drockenmuller

      Version of Record online: 26 APR 2010 | DOI: 10.1002/pola.24018

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      Mn of polytriazoles obtained by polyaddition of a model α-azide-ω-alkyne monomer catalyzed by Cu(PPh3)3Br are limited by the occurrence of a Staudinger side reaction between azide chain-ends and PPh3 ligand from the copper catalyst as shown by SEC, 1H, and 31P NMR experiments. A significant enhancement of Mn could be achieved by using CuIP(OEt)3 as well as optimized dilution and reaction time.

    21. Association of hydrophobically α,ω-end-capped poly(2-methyl-2-oxazoline) in water (pages 2477–2485)

      Gisèle Volet, Anne-Cécile Lasne Deschamps and Catherine Amiel

      Version of Record online: 26 APR 2010 | DOI: 10.1002/pola.24019

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      The α,ω-end-capped poly(2-methyl-2-oxazoline) have been synthesized by a one-pot process using cationic ring-opening polymerization. The polymers bear different alkyl groups C12 and C18. The solution behavior of the amphiphilic polymers has been investigated by SANS, DLS, and pyrene fluorescence. Critical micelle concentrations are dependent on the hydrophilic/lipophilic balance. Intrinsic viscosities are in the same range as the ones of the poly(2-methyl-2-oxazoline) precursors and mono-functionalized polymers. Large viscosity increase corresponding to intermicellar bridging was observed in the vicinity of the micelle overlap concentration. The aggregates were dissociated by addition of hydroxypropyl β-cyclodextrin.

    22. Thermoresponsive super water absorbent hydrogels prepared by frontal polymerization (pages 2486–2490)

      Sergio Scognamillo, Valeria Alzari, Daniele Nuvoli and Alberto Mariani

      Version of Record online: 26 APR 2010 | DOI: 10.1002/pola.24020

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      Super water absorbent hydrogels obtained from acrylamide and 3-sulfopropyl acrylate, potassium salt were prepared by using frontal polymerization. All samples were characterized in terms of their swelling behavior in water at various temperatures. Water contact angle analysis was also performed. It was found that copolymers containing large salt content exhibit a lower critical solution temperature at about 30 °C, which make them potentially interesting stimuli-responsive materials to be used in biomedical applications.

    23. Supramolecular template-directed synthesis of stable and high-efficiency photoluminescence 9,10-diphenylanthryl-bridged ladder polysiloxane (pages 2491–2497)

      Jintao Zhang, Zhize Chen, Wenxin Fu, Ping Xie, Zhibo Li, Shouke Yan and Rongben Zhang

      Version of Record online: 26 APR 2010 | DOI: 10.1002/pola.24021

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      A well-defined 9,10-diphenylanthryl-bridged ladder polysiloxane was synthesized by condensation of a tetrasilanol monomer using the “supramolecular architecture-directed stepwise coupling/polymerization” strategy. The unique double-stranded structure offered obtained ladder polymer good film-forming capability and thermal stability, high fluorescence quantum efficient yield and excellent emission stability, and a low-lying HOMO level. This strategy may contribute to prepare polymeric materials for fabricating the desired stable and high-efficiency optoelectronic devices.

    24. Disassembly via an environmentally friendly and efficient fluorous phase constructed with dendritic architectures (pages 2498–2508)

      Christopher J. Wilson, Daniela A. Wilson, Andrew E. Feiring and Virgil Percec

      Version of Record online: 26 APR 2010 | DOI: 10.1002/pola.24046

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      A new concept for the construction of the fluorous phase based on the amplification of the fluorous effect via dendritic architectures containing very short semifluorinated groups on their periphery is reported. In contrast to dendrons containing perfluoroalkyl groups on their periphery, this new class of semifluorinated dendrons mediates only the disassembly of their parent building blocks from the crystalline state.

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      Cationic polymerization of isobutyl vinyl ether using alcohols both as cationogen and catalyst-modifying reagent: Effect of Lewis acids and alcohols on living nature (pages 2509–2516)

      Arihiro Kanazawa, Shokyoku Kanaoka and Sadahito Aoshima

      Version of Record online: 26 APR 2010 | DOI: 10.1002/pola.24009

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      Controlled cationic polymerization of isobutyl vinyl ether was conducted using MeOH, iPrOH, and tBuOH, with NbCl5, ZrCl4, and SnCl4 as catalysts. The initiating species were generated by reactions between an alcohol and a Lewis acid, giving alkoxy-modified catalytic species. Such modification affected the catalytic activity. Furthermore, the subtle differences in the coordination ability of the alkoxy groups induced two propagating mechanisms: the propagation only with carbon–chlorine bonds or that with both those bonds and acetal structures. The two different pathways were observed with NbCl5 or SnCl4, respectively. In contrast, in the case of polymerization using ZrCl4, MeOH induced the reaction with the dual species, whereas iPrOH and tBuOH produced only by the chloride species.

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