Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 49 Issue 4

15 February 2011

Volume 49, Issue 4

Pages 821–1050

  1. Highlights

    1. Top of page
    2. Highlights
    3. Articles
    4. Rapid Communications
    5. Erratum
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      ADMET: Metathesis polycondensation (pages 821–831)

      Kathleen L. Opper and Kenneth B. Wagener

      Version of Record online: 3 JAN 2011 | DOI: 10.1002/pola.24491

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      Although olefin metathesis has a rich history dating to the 1950s and 1960s, the one particular metathesis mode, Acyclic Diene METathesis (ADMET), has more recent historical roots. The similarity to other metathesis modes that rely on double-bond substituent interchange diverges within ADMET chemistry, an observation that is lesser known. The story regarding the discovery of ADMET chemistry is divulged here.

  2. Articles

    1. Top of page
    2. Highlights
    3. Articles
    4. Rapid Communications
    5. Erratum
    1. Hyperbranched poly(arylene ethynylene)s with triphenylamine core for polymer light-emitting diodes (pages 832–841)

      Akshaya K. Palai, Sarada P. Mishra, Amit Kumar, Ritu Srivastava, Modeeparampil N. Kamalasanan and Manoranjan Patri

      Version of Record online: 14 DEC 2010 | DOI: 10.1002/pola.24459

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      A series of highly fluorescent hyperbranched poly(arylene ethynylene)s (HB-PAEs) were designed and synthesized with triphenylamine as core. Polymers were characterized in terms of their thermal, electrochemical, and optoelectronic properties. Polymer light-emitting devices based on ITO/PEDOT:PSS/HB-PAE/LiF/Al were fabricated and light-emitting properties evaluated.

    2. The suzuki–heck polymerization as a tool for the straightforward obtainment of poly(fluorenylene-vinylene) sensitizers for dye-sensitized solar cells (pages 842–847)

      Roberto Grisorio, Piero Mastrorilli, Gian Paolo Suranna, Pinalysa Cosma, Luisa De Marco, Michele Manca and Giuseppe Gigli

      Version of Record online: 3 JAN 2011 | DOI: 10.1002/pola.24474

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      Poly(arylene-vinylene)s designed for application as dyes in dye-sensitized solar cell were prepared by the Suzuki–Heck polymerization protocol that allowed the insertion of TiO2-anchoring functionalities as well as light harvesting moieties. An excess of potassium vinyltrifluoroborate was used to warrant the obtainment of soluble macromolecules. Used as sensitizers in devices, the materials permitted to reach efficiencies of up to 0.88%.

    3. Degradation of poly(butyl methacrylate) model compounds studied via high-resolution electrospray ionization mass spectrometry (pages 848–861)

      Alexander H. Soeriyadi, Francesca Bennet, Michael R. Whittaker, Philip J. Barker, Christopher Barner-Kowollik and Thomas P. Davis

      Version of Record online: 14 DEC 2010 | DOI: 10.1002/pola.24492

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      A series of p(nBMA), p(t-BMA), and p(HFBMA) model compounds were degraded under weathering conditions imitating extreme environmental conditions. The degradation mechanisms have been mapped via high-resolution ESI-MS.

    4. Synthesis of octahedral zirconium complex bearing [NHC[BOND]O] ligands, and its behavior as catalyst in the polymerization of olefins (pages 862–870)

      Carmen Bocchino, Mariagrazia Napoli, Chiara Costabile and Pasquale Longo

      Version of Record online: 14 DEC 2010 | DOI: 10.1002/pola.24495

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      The synthesis and characterization of a zirconium complex, having two alkoxide functionalized N-heterocyclic carbene ligands [NHC[BOND]O], and its behavior as catalyst in the polymerization of ethylene and propylene, have been reported. Linear polyethylene having a high Mw and a polydispersity index (MDI) > 2, and polypropylene highly isotactic together with an atactic fraction were obtained. DFT studies on the complex stereoisomer stability gave indications on the species possibly involved in the polymerizations.

    5. Self-assembly of di- and triblock PEG-pentavaline amphiphiles (pages 871–878)

      Elizabeth E. Hwang, Taylor R. Wilson-Hill, Ji Won Ahn, Andrew P. Platt, Katherine E. Rutledge and Sarah L. Goh

      Version of Record online: 8 DEC 2010 | DOI: 10.1002/pola.24497

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      Fmoc-capped pentavaline sequences were conjugated to either mono or dihydroxy functionalized poly(ethylene glycol) (PEG) to generate a small family of di- and tri-block copolymers with molecular weights ranging from 3 to 16.4 kDa. β-sheet formation of the pentavaline domains drives the self-assemble in aqueous solution to form spherical particles, with critical aggregation concentrations of 0.46–16.29 μM and diameters of 33–127 nm. Circular dichroism and dynamic light scattering studies confirm that these aggregates are stable up to 80 °C.

    6. Ring-opening metathesis polymerization of cis-cyanocyclooct-4-ene: Search for active catalysts, variation of monomer to catalyst ratios and monomer concentrations (pages 879–885)

      Martin F. Schneider, Carola Gantner, Werner Obrecht and Oskar Nuyken

      Version of Record online: 8 DEC 2010 | DOI: 10.1002/pola.24498

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      Ruthenium-based catalysts of the first, second, and third generation were used for the ring-opening metathesis polymerization of cis-cyanocyclooct-4-ene. Contrary to second and third generation catalysts, first generation catalysts were not active. The second generation catalyst [RuCl2([DOUBLE BOND]CHPh)(H2IMes)(PCy3)] (H2IMes = N,N′-bis(mesityl)-4,5-dihydroimidazol-2-ylidene) showed low initiation rates and polymer degradation. A variation of monomer to catalyst ratios revealed nonlinear relationships between degree of polymerization and monomer conversion. Also, the critical monomer concentration was determined below which no polymerization occurred. However, for the third generation catalysts, fast initiation rates and no polymer degradation was observed.

    7. Block-brush copolymers via ROMP and sequential double click reaction strategy (pages 886–892)

      Aydan Dag, Hatice Sahin, Hakan Durmaz, Gurkan Hizal and Umit Tunca

      Version of Record online: 8 DEC 2010 | DOI: 10.1002/pola.24499

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      The living ROMP of oxanorbornene (ONB) affords the synthesis of well-defined poly (ONB-anthracene)20-b-poly(ONB-azide)5 block copolymer with anthryl and azide pendant groups. Subsequently, well-defined linear alkyne end-functionalized PCL (PCL-alkyne), maleimide end-functionalized PMMA (PMMA-MI) and poly(tert-butyl acrylate) (PtBA-MI) were introduced onto the block copolymer via sequential azide-alkyne and Diels-Alder click reactions, thus yielding block-brush copolymers: poly(ONB-g-PMMA)-b-poly(ONB-g-PCL) and poly(ONB-g-PtBA)-b-poly(ONB-g-PCL).

    8. Blue fluorescent polyamides containing naphthalene and oxadiazole rings (pages 893–906)

      Mariana-Dana Damaceanu, Radu-Dan Rusu, Alina Nicolescu and Maria Bruma

      Version of Record online: 14 DEC 2010 | DOI: 10.1002/pola.24500

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      The combination of several structural modifications, that is, the incorporation of 1,3,4-oxadiazole rings, naphthalene units, and flexible groups in the polymer backbones, minimizes the trade-off between processability and properties of wholly aromatic polyamides. High-performance poly(oxadiazole-amide)s based on a new monomer containing 1,3,4-oxadiazole and naphthalene moieties and three different diacid chlorides containing solubility improving flexible groups, with potential applications in electroluminescent devices, were successfully synthesized. The properties of these polymers such as solubility, molecular weights, thermal stability, glass transition temperature, photo-optical and electrochemical properties, as well as the quality of the thin films obtained from these polymers were investigated.

    9. Boron-functionalized poly(3-hydroxybutyrate)s from hydroboration of poly(allyl-β-hydroxyalkanoate)s: Synthesis and insights into the microstructure (pages 907–917)

      Clémence Guillaume, Noureddine Ajellal, Jean-François Carpentier and Sophie M. Guillaume

      Version of Record online: 10 DEC 2010 | DOI: 10.1002/pola.24502

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      Syndiotactic-enriched and isotactic-enriched allyl- and boronate-functionalized poly(3-hydroxybutyrate)s have been prepared from the ring-opening polymerization of racemic allyl-β-butyrolactone mediated by discrete yttrium or zinc catalysts, followed by rhodium-catalyzed hydroboration using pinacolborane. The microstructure of the poly(hydroxyalkanoate)s in relation to the metallic system involved has been investigated in details.

    10. Atom transfer radical polymerization of functional monomers employing Cu-based catalysts at low concentration: Polymerization of glycidyl methacrylate (pages 918–925)

      Nicolay V. Tsarevsky and Wojciech Jakubowski

      Version of Record online: 10 DEC 2010 | DOI: 10.1002/pola.24503

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      Activators regenerated by electron transfer and initiators for continuous activator regeneration (ICAR) atom transfer radical polymerizations (ATRPs) were used to polymerize glycidyl methacrylate (GMA). The reducing agent employed in the former method participated in side reactions (epoxide ring opening), which led to poorly defined polymers. ICAR ATRP, in contrast, was successfully used to prepare well-defined polymers with controlled molecular weights (up to ca. 50,000 g mol−1) and narrow molecular weight distributions (Mw/Mn < 1.25). The copper complex of tris(2-pyridylmethyl)amine was used as the catalyst in the ICAR ATRP of GMA at about 105 ppm. The ICAR ATRP procedures were used to prepare block copolymers by chain-extension of poly(methyl methacrylate) macroinitiator.

    11. Synthesis and phase-separation behavior of α,ω-difunctionalized diblock copolymers (pages 926–937)

      Saija Werner, Doris Pospiech, Dieter Jehnichen, Kathrin Eckstein, Hartmut Komber, Peter Friedel, Andreas Janke, Franziskus Näther, Uta Reuter, Brigitte Voit, Rosa Taurino and Massimo Messori

      Version of Record online: 17 DEC 2010 | DOI: 10.1002/pola.24505

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      A series of poly(pentyl methacrylate-b-methyl methacrylate) block copolymers with allyl groups at different positions was prepared to generate perpendicular (standing) morphologies in thin films on silicon substrates via specific interactions. Living anionic polymerization with functional initiators and/or allyl bromide termination followed by subsequent conversion of allyl into OH-groups via hydroboration is described. The morphology is weakly influenced by OH-groups (alteration of d-spacing L0). Introduction of OH-groups together with small df/L0 ratio proved as necessary condition for formation of standing lamellae morphologies in thin films. OH-terminated BCP acted as template for generation of silica nanoparticles in thin hybrid films.

    12. Preparation of cycloolefin copolymers of a bulky tricyclopentadiene (pages 938–944)

      Hyeong Cheol Park, Ahreum Kim and Bun Yeoul Lee

      Version of Record online: 17 DEC 2010 | DOI: 10.1002/pola.24506

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      Copolymerizations of ethylene and tricyclopentadiene (TCPD) are realized without formation of a gel using a catalytic system of [Ph2C(Flu)(Cp)]ZrCl2/MMAO. Successive TCPD insertions are not allowed and 41 mol % is the attained highest TCPD content in the copolymer, which exhibits a high Tg of 214 °C. It shows the highest Tg at an identical cycloolefin mole % among the reported cycloolefin copolymers. The remaining double bond can be hydrogenated or converted to an epoxide group.

    13. A photo-degradable helix: Synthesis, structure, and photolysis of optically active poly[2,7-bis(4-t-butylphenyl)-9-methylfluoren-9-yl acrylate] (pages 945–956)

      Takeshi Sakamoto, Kento Watanabe, Yukatsu Shichibu, Katsuaki Konishi, Shin-Ichiro Sato and Tamaki Nakano

      Version of Record online: 17 DEC 2010 | DOI: 10.1002/pola.24507

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      BBPMFA, a new bulky acrylate, affords a preferred-handed, optically active polymer by asymmetric anionic polymerization. Poly(BBPMFA) is very sensitive to light and completely decomposes into poly(acrylic acid) and 2,7-bis(4-t-butylphenyl)dibenzofulvene within one second on irradiation using an Hg-Xe lamp. The reaction seems to proceed through an unzipping mechanism where once an ester bonding is cleaved in a chain (the initial cleavage), successive cleavage reactions along the entire chain proceeds from the initial cleavage point at a much large rate than that of the initial cleavage. The photolysis of poly(BBPMFA) may be one of the fastest reaction for synthetic polymers.

    14. Synthesis of polyethylene-grafted multiwalled carbon nanotubes via a peroxide-initiating radical coupling reaction and by using well-defined TEMPO and thiol end-functionalized polyethylenes (pages 957–965)

      Sohaib Akbar, Emmanuel Beyou, Philippe Chaumont, Jérôme Mazzolini, Edgar Espinosa, Franck D'agosto and Christophe Boisson

      Version of Record online: 3 JAN 2011 | DOI: 10.1002/pola.24508

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      PE-grafted MWCNTs core–shell nanostructures were synthesized from polyethylene, TEMPO- and thiol-terminated polyethylenes by a radical process at 160 °C in 1,3-dichlorobenzene as solvent. The chain-end reactivity of TEMPO- and thiol-terminated polyethylenes permitted to obtain PE grafting densities around 2.5 mg m−2.

    15. Synthesis of backbone thermo and pH dual-responsive hyperbranched poly(amine-ether)s through proton-transfer polymerization (pages 966–975)

      Yan Pang, Qi Zhu, Dongliang Zhou, Jinyao Liu, Yan Chen, Yue Su, Deyue Yan, Xinyuan Zhu and Bangshang Zhu

      Version of Record online: 17 DEC 2010 | DOI: 10.1002/pola.24509

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      Novel backbone thermo and pH dual-responsive hyperbranched poly(amine-ether)s were prepared successfully in one-pot through proton-transfer polymerization of triethanolamine and 1,2,7,8-diepoxyoctane with the help of potassium hydride. The LCSTs were depended on the polymer composition as well as the concentration and pH values of polymer aqueous solution. In vitro evaluation demonstrated their low cytotoxicity and efficient cell internalization. All results show that these thermo and pH dual-responsive hyperbranched poly(amine-ether)s are promising materials for biomedical application.

    16. Synthesis and properties of bio-based polyurethanes bearing hydroxy groups derived from alditols (pages 976–985)

      Kazuhiko Hashimoto, Naoya Hashimoto, Takehiko Kamaya, Junya Yoshioka and Haruki Okawa

      Version of Record online: 3 JAN 2011 | DOI: 10.1002/pola.24510

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      Bio-based polyurethanes bearing two or four hydroxy groups in the pendants were synthesized by the polyaddition of D-mannitol- and D,L-erythritol-derived diols with lysine-derived diisocyanate and hexamethylene diisocyanate and the subsequent deprotection of the isopropylidene groups. From the hydrolytic tests at 50 °C and pH 7.0, the hydroxy groups in the polyurethanes was found to enhance their hydrolyzability significantly, although the degradation rate was lower than that of the polyurethanes containing lactone groups reported in our previous articles. The introduction of D-mannitol units to the polyether-polyurethanes containing poly(oxytetramethylene) glycol units also led to control the hydrolytic degradation.

    17. Synthesis of a variety of star-shaped polybenzamides via chain-growth condensation polymerization with tetrafunctional porphyrin initiator (pages 986–994)

      Kazuo Yoshino, Akihiro Yokoyama and Tsutomu Yokozawa

      Version of Record online: 3 JAN 2011 | DOI: 10.1002/pola.24511

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      A variety of well-defined tetra-armed star-shaped poly(N-substituted p-benzamide)s, including block poly(p-benzamide)s with different N-substituent groups, and poly(N-substituted m-benzamide)s were synthesized by using a porphyrin-cored tetra-functional initiator under optimized polymerization conditions.

    18. Syntheses of random PET-co-PTTs and some related copolyesters by entropically-driven ring-opening polymerizations and by melt blending: Thermal properties and crystallinity (pages 995–1005)

      Lucia Conzatti, Matteo Alessi, Paola Stagnaro and Philip Hodge

      Version of Record online: 3 JAN 2011 | DOI: 10.1002/pola.24513

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      A library of PET, PTT, and seven PET–PTT copolymers has been prepared in a high throughput manner by entropically-driven ring-opening polymerizations or copolymerizations of the corresponding macrocyclic oligomers. The thermal properties have been investigated, and it has been shown that the 50:50 copolymer displays a crystalline phase. The same phase can be formed by in situ transesterifications when a 50:50 mixture of PET and PTT is melt blended. PBT–PET and PTT–PBT 50:50 copolymers also show crystal phases.

    19. Vanadium alkoxide catalyzed polymerization of vinyl chloride (pages 1006–1012)

      Yoshikatsu Tsuchiya and Kiyoshi Endo

      Version of Record online: 3 JAN 2011 | DOI: 10.1002/pola.24514

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      Effect of cocatalyst, solvent, and cocatalyst/precatalyst ratio on polymerization of vinyl chloride (VC) with vanadium complex/alkylaluminum catalysts was studied. Polymerization activity of VO(OEt)3/Al(i-Bu)3 was about seven times higher than that of Cp*Ti(OPh)3/MAO catalyst which was previously reported. VO(OEt)3/alkylaluminum catalyst was also able to copolymerize VC with styrene, 1-butene, methyl methacrylate, and methyl acrylate.

    20. Microwave-assisted TCNE/TCNQ addition to poly(thienyleneethynylene) derivative for construction of donor–acceptor chromophores (pages 1013–1020)

      Yuping Yuan, Tsuyoshi Michinobu, Minoru Ashizawa and Takehiko Mori

      Version of Record online: 3 JAN 2011 | DOI: 10.1002/pola.24515

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      Small cyano-containing acceptor molecules, such as tetracyanoethylene and tetracyanoquinodimethane, underwent the addition reaction with the alkyne moieties of the poly(thienyleneethynylene) derivative under microwave irradiation, which produced donor–acceptor-type polymers with enhanced I2-doped conductivities.

    21. Controlled polymerization of carbazole-based vinyl and methacrylate monomers at ambient temperature: A comparative study through ATRP, SET, and SET-RAFT polymerizations (pages 1021–1032)

      Neelamegan Haridharan and Raghavachari Dhamodharan

      Version of Record online: 3 JAN 2011 | DOI: 10.1002/pola.24518

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      Controlled radical polymerization of carbazole based monomers, N-vinylcarbazole (NVK) and carbazole methacrylate (CMA) at ambient temperature, is successfully demonstrated via SET-RAFT. For this purpose, CMA a novel, carbazole based monomer and a trithiocarbonate chaintransfer agent (CTA) comprising of butane thiol with carboxylic acid as the end group were synthesized and characterized. The polymerization is observed to be less controlled under SET and ATRP conditions and more controlled under SET-RAFT conditions, at ambient temperature. Novel diblock copolymers P(CMA-b-FMA) and P(NVK-b-FMA) are synthesized from the macroinitiators.

    22. Nitroxide-mediated radical copolymerization of methyl methacrylate controlled with a minimal amount of 9-(4-vinylbenzyl)-9H-carbazole (pages 1033–1045)

      Benoit Lessard, Edwin Jee Yang Ling, Marie Sylvianne Thérèse Morin and Milan Marić

      Version of Record online: 3 JAN 2011 | DOI: 10.1002/pola.24522

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      Poly(methacrylates) are valued for their excellent optical and mechanical properties. Currently, their synthesis using nitroxide-mediated radical copolymerization is problematic without the use of a comonomer (which in some cases can impair the final characteristics of the copolymer) to increase the polymerization control and keep the molecular weight distribution narrow. 9-(4-Vinylbenzyl)-9H-carbazole (VBK) was used as a comonomer with hole-transport properties. In addition to introducing the carbazole unit into the methacrylate chain, less VBK was required (as little as 1 mol %, which is lower than the 4.4–8.8 mol % required using styrene as a comonomer) to obtain a controlled polymerization, resulting in final copolymers with narrow molecular weight distributions (Mw/Mn ≈ 1.3).

  3. Rapid Communications

    1. Top of page
    2. Highlights
    3. Articles
    4. Rapid Communications
    5. Erratum
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      Atom transfer radical polymerization using activators regenerated by electron transfer of acrylonitrile in 1-(1-ethoxycarbonylethyl)-3-methylimidazolium hexafluorophospate (pages 1046–1049)

      Hou Chen, Lingfang Chen, Chunhua Wang and Rongjun Qu

      Version of Record online: 17 DEC 2010 | DOI: 10.1002/pola.24512

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      Atom transfer radical polymerization using activators regenerated by electron transfer (ARGET ATRP) of acrylonitrile (AN) was first approached with 1-(1-ethoxycarbonylethyl)-3-methylimidazolium hexafluorophospate ([ecemim][PF6]) as reaction medium and tin(II) bis(2-ethylhexanoate) (Sn(EH)2) as reducing agent in the presence of air. When compared with in bulk, an obvious increase of polymer isotacticity was observed for ARGET ATRP of AN in [ecemim][PF6], the reaction rate of ARGET ATRP of AN in [ecemim][PF6] was higher and the polymerization process was better controlled. The block copolymer polyacrylonitrile-block-poly(methyl methacrylate) with molecular weight at 69,750, distribution at 1.34 and isotacticity at 0.36 was successfully obtained in [ecemim][PF6]. [Ecemim][PF6] and the catalyst system were recycled and reused and had no effect on the living nature of polymerization.

  4. Erratum

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    2. Highlights
    3. Articles
    4. Rapid Communications
    5. Erratum
    1. You have free access to this content

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