Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 48 Issue 12

15 June 2010

Volume 48, Issue 12

Pages 2517–2731

  1. Articles

    1. Top of page
    2. Articles
    3. Notes
    1. Kinetic investigation of the RAFT polymerization of p-acetoxystyrene (pages 2517–2524)

      Solène I. Cauët and Karen L. Wooley

      Version of Record online: 13 MAY 2010 | DOI: 10.1002/pola.24024

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      The kinetics of the RAFT polymerization of p-acetoxystyrene using a trithiocarbonate chain transfer agent, S-1-dodecyl-S′-(α,α′-dimethyl-α″-acetic acid)trithiocarbonate, DDMAT, was investigated. Parameters including temperature, percentage initiator, concentration, monomer-to-chain transfer agent ratio, and solvent were varied and their impact on the rate of polymerization and quality of the final polymer were examined.

    2. Synthesis, characterization, and heterogeneous catalysis of polymer-supported poly(propyleneimine) dendrimer stabilized gold nanoparticle catalyst (pages 2525–2532)

      Eagambaram Murugan and Rajmohan Rangasamy

      Version of Record online: 13 MAY 2010 | DOI: 10.1002/pola.24028

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      Heterogeneous gold nanoparticle (AuNPs) catalysts were prepared via immobilization of AuNPs on to the dendrimer grafted crosslinked bead shaped polymer-supported poly(4-vinylpyridine) matrix. The catalytic potential of these AuNPs immobilized nanoparticle catalysts is found to be excellent for the reduction of 4-nitrophenol. They can also be reused by simple filtration and the activity was found to be not changed up to many cycles that shows their stability.

    3. Functional polyisobutylenes via a click chemistry approach (pages 2533–2545)

      Nemesio Martinez-Castro, Andrew J. D. Magenau and Robson F. Storey

      Version of Record online: 13 MAY 2010 | DOI: 10.1002/pola.24029

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      Azide-functional polyisobutylenes were synthesized by quenching of quasiliving PIB with a 1-(ω-haloalkyl)pyrrole, followed by substitution with azide ion or quenching directly with a 1-(ω-azidoalkyl)pyrrole. 1H NMR analysis revealed mixed end groups in which PIB was attached at either C2 or C3 of the pyrrole ring (C2/C3 = 0.40/0.60). SEC indicated the absence of coupled PIB under optimized conditions, confirming exclusive mono-substitution on each pyrrole ring. Azide-terminated PIBs were reacted in modular fashion with various alkynes via 1,3-dipolar cycloaddition, using Cu(I) catalyst. Reactions were quantitative producing PIBs bearing terminal hydroxyl, acrylate, glycidyl, or dimethylaminomethyl groups attached via exclusively 4-substituted triazole linkages.

    4. Maleimide-based thiol reactive multiarm star polymers via Diels-Alder/retro Diels-Alder strategy (pages 2546–2556)

      Ozgul Gok, Hakan Durmaz, Emrah Soner Ozdes, Gurkan Hizal, Umit Tunca and Amitav Sanyal

      Version of Record online: 13 MAY 2010 | DOI: 10.1002/pola.24030

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      Multiarm star polymers containing thiol-reactive maleimide groups at their core have been synthesized using a masked maleimide containing multiarm dendritic initiator. Unmasking of the maleimide group after the polymerization provides multiarm polymers with a reactive core that is readily functionalized via Michael type thiol-ene conjugation.

    5. Ring-opening metathesis copolymerization of cyclooctene and a carborane-containing oxanorbornene (pages 2557–2563)

      Yoan C. Simon and E. Bryan Coughlin

      Version of Record online: 13 MAY 2010 | DOI: 10.1002/pola.24032

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      Copolymers of cyclooctene and a silyl-protected oxanorbornene imide carborane have been obtained with varying compositions. The thermal and structural properties of these polymers have been evaluated and compared with model compounds.

    6. Water-soluble triply-responsive homopolymers of N,N-dimethylaminoethyl methacrylate with a terminal azobenzene moiety (pages 2564–2570)

      Xinde Tang, Xiaochao Liang, Longcheng Gao, Xinghe Fan and Qifeng Zhou

      Version of Record online: 13 MAY 2010 | DOI: 10.1002/pola.24034

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      Water-soluble triply-responsive Azo-PDMAEMA homopolymers were synthesized by ATRP. The LCST of the homopolymers can be modulated by the pH of aqueous solution and/or by light. The terminal azobenzene moiety can undergo reversible photoisomerization under alternative UV/visible light irradiation, which results in a changeable hydrophilicity in aqueous solution. Such homopolymers combine pH, photo-, and thermoresponsive properties in a single macromolecule, and exhibit triple-stimuli responsivity.

    7. Conjugated polymers with broad absorption: Synthesis and application in polymer solar cells (pages 2571–2578)

      Jinsheng Song, Chi Zhang, Cuihong Li, Weiwei Li, Ruiping Qin, Binsong Li, Zhengping Liu and Zhishan Bo

      Version of Record online: 13 MAY 2010 | DOI: 10.1002/pola.24035

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      A series of main chain donor-acceptor low-bandgap conjugated polymers were designed, synthesized; the polymers in films exhibited broad absorption ranging from 300 to 1000 nm with optical bandgaps of around 1.40 eV. Photovoltaic devices based on polymer/PC61BM blends were fabricated by spin-coating from dichlorobenzene. With 1,8-diiodooctane as an additive, device based on polymer P1 shows the best PCE of 2.44%.

    8. Modeling multiphase latex particle equilibrium morphology (pages 2579–2583)

      Yuri Reyes and José M. Asua

      Version of Record online: 13 MAY 2010 | DOI: 10.1002/pola.24036

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      Multiphase waterborne polymer particles provide advantages in the more demanding applications and their performance depends on particle morphology. Currently, no general approach to predict the morphology of multiphase latex particles is available. In this work, a general model based on Monte Carlo simulation was developed for the prediction of equilibrium morphologies of multiphase waterborne systems, such as polymer-polymer and polymer-polymer-inorganic hybrids.

    9. Structure and surface properties of polyacrylates with short fluorocarbon side chain: Role of the main chain and spacer group (pages 2584–2593)

      Qiongyan Wang, Qinghua Zhang, Xiaoli Zhan and Fengqiu Chen

      Version of Record online: 13 MAY 2010 | DOI: 10.1002/pola.24038

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      The chemical composition of main chain and spacer group was found to have prominent effects on bulk organization and surface properties of polyacrylates with perfluoroalkyl side chain. Poly[(perfluorohexyl) ethyl] acrylate (PC6A) was found to be amorphous and showed poor dynamic water repellency. However, with the same perfluoroalkyl chain length, poly[2-[[[[2-(perfluorohexyl)]sulfonyl]methyl]amino]ethyl] acrylate and methacrylate exhibited liquid crystalline lamellar structures in the bulk and provided with excellent dynamic surface properties. Although poly[(perfluorohexyl)ethyl] methacrylate (PC6MA) was amorphous, its dynamic water repellency was better than the one of PC6A. This phenomenon was probably attributed to the low mobility of the side chain because of its high glass transfer temperature of PC6MA.

    10. Pyrromethene derivatives in three-component photoinitiating systems for free radical photopolymerization (pages 2594–2603)

      O. I. Tarzi, X. Allonas, C. Ley and J.-P. Fouassier

      Version of Record online: 13 MAY 2010 | DOI: 10.1002/pola.24039

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      The presence of redox additives in a pyrromethene-based photoinitiating system allows an important increase of the free radical photopolymerization efficiency.

    11. Highly refractive polymer resin derived from sulfur-containing aromatic acrylate (pages 2604–2609)

      Nam-Ho You, Tomoya Higashihara, Shinji Ando and Mitsuru Ueda

      Version of Record online: 13 MAY 2010 | DOI: 10.1002/pola.24040

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      New sulfur-containing polymers with high-refractive indices and low birefringences have been developed as UV-curable high-refractive polymer resins. The polymer resins show high transparency in the visible region and good thermal stability, such as 5% weight-loss temperatures at 355 °C under nitrogen and glass transition temperatures (Tg) in the range of 94–143 °C. They showed high-refractive indices of 1.6531 and 1.6645 at 632.8 nm, and low birefringences of 0.0039 and 0.0069, respectively.

    12. Free radical and nitroxide mediated polymerization of hydroxy–functional acrylates prepared via lipase–catalyzed transacylation reactions (pages 2610–2621)

      Dragos Popescu, Richard Hoogenboom, Helmut Keul and Martin Möller

      Version of Record online: 13 MAY 2010 | DOI: 10.1002/pola.24041

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      Various hydroxy functional polyacrylates were prepared by a cascade of lipase-catalyzed transacylation and free radical or nitroxide mediated polymerization. The NMP polymerization kinetics are discussed as well as the effect of the polymerization method on the resulting polyacrylates.

    13. An efficient way to tune grafting density of well-defined copolymers via an unusual Br-containing acrylate monomer (pages 2622–2630)

      Yaqin Zhang, Yaogong Li, Yongjun Li, Dong Yang, Jianhua Hu, Guolin Lu and Xiaoyu Huang

      Version of Record online: 13 MAY 2010 | DOI: 10.1002/pola.24042

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      An unusual Br-containing acrylate monomer, tert-butyl 2-((2-bromopropanoyl-oxy)methyl)acrylate, is involved in synthesizing grafting-density-controllable PtBA-g-PBA well-defined graft copolymers via sequential RAFT and ATRP without any postpolymerization functionality modification.

    14. Modifications of the active sites distribution in the Ziegler-Natta polymerization of propylene using Lewis acids (pages 2631–2635)

      David Ribour, Roger Spitz and Vincent Monteil

      Version of Record online: 14 MAY 2010 | DOI: 10.1002/pola.24043

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      Heterogeneous Ziegler-Natta precatalysts were modified by treatments with various Lewis acids (MCln with M = Ga, Sn, Si, and Sb and n = 3, 4, or 5) before their use in the polymerization of propylene. Performed on previously “detitanated” precatalysts or on unmodified precatalysts, treatments with SnCl4 and SiCl4 lead to a slight activation but especially to an increase of the tacticity (and/or of Tm) whereas GaCl3 and SbCl5 treatments deactivate the catalyst. A narrowing of the molecular weight distribution is observed in the case of SnCl4 and SiCl4 treatments on unmodified precatalysts.

    15. Facile one-pot synthesis of linear and radial block copolymers of styrene and isoprene through a novel coupling agent by living anionic polymerization (pages 2636–2641)

      Santosh Kumar, Priyank N. Shah, Beom-Goo Kang, Joon-Keun Min, Woon Sung Hwang, Ik Kyung Sung, Shailesh R. Shah, Chivukula N. Murthy, Seonyoung Ahn, Taihyun Chang and Jae-Suk Lee

      Version of Record online: 14 MAY 2010 | DOI: 10.1002/pola.24044

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      The three different block copolymers, di-, tri-, and three-armed star-block of styrene and isoprene were synthesized with a control in terms of their molecular weight and weight fractions through a new methodology using living anionic polymerization. Because of the abstraction of hydrogen from the active methylene group of MC by the living diblock, a new tri-functional coupling agent (MC-1) is generated in situ, and this coupling agent allows the formation of star-block copolymer as well.

    16. Poly(N-vinylcarbazole) chemically modified graphene oxide (pages 2642–2649)

      Bin Zhang, Yu Chen, Xiaodong Zhuang, Gang Liu, Bo Yu, En-Tang Kang, Jinhui Zhu and Yongxi Li

      Version of Record online: 14 MAY 2010 | DOI: 10.1002/pola.24047

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      A new soluble donor-acceptor type poly(N-vinylcarbazole)-covalently functionalized graphene oxide (GO-PVK) is synthesized by reaction of DDAT-PVK with GO-TDI. The incorporation of sufficient amount of PVK chains makes the modified GO nanosheets readily dispersible in organic solvents. The resulting material exhibits an enhanced solubility of 10 mg/mL in organic solvents and a significant energy bandgap of ∼2.0 eV. The intensity of the emission band of GO-PVK at 437 nm is a little bit quenched when compared to that of DDAT-PVK suggesting intramolecular quenching from PVK to GO.

    17. Cationic polymerization of L,L-lactide (pages 2650–2658)

      Małgorzata Baśko and Przemysław Kubisa

      Version of Record online: 14 MAY 2010 | DOI: 10.1002/pola.24048

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      Polylactide obtained by cationic bulk polymerization initiated by trifluoromethanesufonic acid shows considerably higher thermal and hydrolytic stability than polylactide of comparable molecular weight obtained with ROH/Sn(Oct)2 initiating system. Cationic polymerization of lactide initiated by strong acid proceeds by activated monomer mechanism. According to this mechanism, growing macromolecules are fitted with terminal [BOND]OH and [BOND]C(O)OSO2CF3 end-groups. The presence of those groups allows efficient end-to-end cyclization. Cyclic nature of resulting polylactide explains its higher thermal and hydrolytic stability as compared with linear polylactide.

    18. New poly(phenylenevinylene)-methyl methacrylate-based photonic crystals (pages 2659–2665)

      Sylvain Achelle, Álvaro Blanco, Martín López-García, Riccardo Sapienza, Marta Ibisate, Cefe López and Julián Rodríguez-López

      Version of Record online: 14 MAY 2010 | DOI: 10.1002/pola.24049

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      A series of monodisperse colloids was prepared by copolymerization of methyl methacrylate and fluorescent first- and second-generation poly(phenylenevinylene) dendrons under surfactant-free emulsion polymerization conditions. The copolymers were microspheres with smooth surfaces and narrow dispersity. The changes in the monomer/water ratio enabled the sizes of the beads to be varied. The materials can be crystallized into polymer opal photonic crystals, and the emission is not affected by the periodic structure because of the large spectral distance between the emission and the pseudogap position.

    19. Reactivities of carbocations and monomers in carbocationic polymerization and copolymerization (pages 2666–2680)

      Pierre Sigwalt and Michel Moreau

      Version of Record online: 14 MAY 2010 | DOI: 10.1002/pola.24051

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      For living carbocationic polymerizations, propagation rate constants kp± obtained by the diffusion-clock method for 4-methylstyrene (pMeSt) and styrene (St) are also controlled by diffusion (kp± = 109–3 × 109 L mol−1 s−1) while those obtained from the ionic species concentration for 2,4,6-trimethylstyrene and 4-methoxystyrene are about 104 to 105. This has been attributed to the much larger electrophilicity of the St and pMeSt carbocations, but it is concluded that they result from the different method used. Diffusion controlled propagation for pMeSt and St is shown incompatible with the copolymerization results of pClSt, St, pMeSt, and pMeOSt, which are in agreement with approximately inverse reactivities between a monomer and the corresponding carbocation leading to similar kp± for all styrenes (∼105).

    20. Unexpected alternating radical copolymerization of chlorotrifluoroethylene with 3-isopropenyl-α,α′-dimethylbenzyl isocyanate (pages 2681–2697)

      M. Kyulavska, G. Kostov, B. Ameduri and R. Mateva

      Version of Record online: 14 MAY 2010 | DOI: 10.1002/pola.24052

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      Free radical copolymerization of chlorotrifluoroethylene and 3-isopropenyl-α,α′-dimethylbenzyl isocyanate was successfully achieved in radical conditions and the reactivity ratios were determined rCTFE = 0.076 ± 0.021 and rm-TMI = 0.034 ± 0.028 at 130 °C.

    21. Evaluation of peroxide initiators for radical polymerization-based self-healing applications (pages 2698–2708)

      Gerald O. Wilson, James W. Henderson, Mary M. Caruso, Benjamin J. Blaiszik, Patrick J. McIntire, Nancy R. Sottos, Scott R. White and Jeffrey S. Moore

      Version of Record online: 14 MAY 2010 | DOI: 10.1002/pola.24053

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      Electron micrograph of a PMMA bone cement fracture surface containing microcapsules of BPO in initiator in the solvent phenyl acetate. The capsules were mixed into bone cement and then fractured on a load frame to reveal ruptured capsules on the fracture plane.

    22. Synthesis of phenanthroline-terminated polymers and their Fe(II)-complexes (pages 2709–2715)

      Miklós Nagy, Miklós Zsuga, Dávid Rácz and Sándor Kéki

      Version of Record online: 14 MAY 2010 | DOI: 10.1002/pola.24054

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      Phenanthroline-terminated PEGs and PIBs capable of polymer network formation were prepared. The polymers underwent quantitative complex formation with ferrous ions in solution. All of the complexes are soluble and stable in nonpolar solvents such as methylene chloride and even in hexane (PIB-phen complexes).

    23. Immortal SET–LRP mediated by Cu(0) wire (pages 2716–2721)

      Xuan Jiang, Brad M. Rosen and Virgil Percec

      Version of Record online: 14 MAY 2010 | DOI: 10.1002/pola.24059

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      Cu(0)-wire/Me6-TREN is a well established catalyst for living radical polymerization via SET–LRP. Here, it is demonstrated that this polymerization is not just living, but is in fact the first example of immortal radical polymerization. The immortality of SET–LRP mediated with Cu(0) wire was demonstrated by attempting, unsuccessful, to kill the polymerization via exposure O2. The polymerization stopped when the reaction mixtures were exposed to air. The reactions, however, reached high conversion after resealing the reaction vessel and reestablishing the catalytic cycle of the SET–LRP with Cu(0) wire.

  2. Notes

    1. Top of page
    2. Articles
    3. Notes
    1. You have free access to this content
      Synthesis and polymerization of novel bis(2-trifluoromethylacrylate) (pages 2722–2724)

      Genki Kurakami, Akihiro Hosoya, Hiroshi Hamana and Tadashi Narita

      Version of Record online: 14 MAY 2010 | DOI: 10.1002/pola.24037

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      Syntheses and radical polymerizations of novel ethylene 2-trifluoromethylacrylate [(CH2[DOUBLE BOND]C(CF3)COOCH2CH2OCOC(CF3)[DOUBLE BOND]CH2] was examined in the presence of 1,4-dioxane to afford a polymer possessing the molecular weight of as high as 5.6 × 104 possessing 1,4-dioxane moieties in side chains although radical addition polymerization of 2-trifluoromethylacrylate hardly takes place. The 5 wt % loss temperature of the polymer was 309 °C determined by thermogravimetric analysis.

    2. You have free access to this content
      Preparation of sulfonated crosslinked poly(2,6-dimethyl-1,4-phenylene oxide) membranes for direct methanol fuel cells by using electron beam irradiation (pages 2725–2731)

      Jung-Soo Lee, Chan-Hee Jung, Su-Yeon Jo, Jae-Hak Choi, In-Tae Hwang, Young-Chang Nho, Young-Moo Lee and Jae-Suk Lee

      Version of Record online: 14 MAY 2010 | DOI: 10.1002/pola.24045

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      Sulfonated crosslinked poly(2,6-dimethyl-1,4-phenlylene oxide) (PPO) were successfully fabricated via electron beam irradiation followed by sulfonation and evaluated for direct methanol fuel cell (DMFC) applications. The thermal and mechanical properties were improved by the formation of crosslinked networks in the PPO membranes. The sulfonated crosslinked PPO (CPPO) membranes exhibited better ion exchange capacity and proton conductivity than the Nafion 115. The methanol permeability of the sulfonated CPPO membranes was effectively reduced without sacrificing other properties. Thus, these membranes could be used as a new proton exchange membrane for DMFC applications.