Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 45 Issue 21

1 November 2007

Volume 45, Issue 21

Pages 4751–5030

  1. Highlights

    1. Top of page
    2. Highlights
    3. Articles
    4. Notes
    1. You have free access to this content
      Condensation routes to polyaniline and its analogs (pages 4751–4763)

      H. K. Hall, Jr., Anne B. Padias and Harold W. Boone

      Version of Record online: 12 SEP 2007 | DOI: 10.1002/pola.22353

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      This highlight describes polycondensation as a possible route to polyanilines which are more structurally perfect than those obtainable by the oxidation of anilines. Condensation of anthraquinones with aromatic diamines using titanium tetrachloride and Dabco gave high molecular weight orange polyquinonimines. Appropriately positioned alkoxy groups afforded stereoregular polymers. Application of the same procedure to 2,5-dimethyl-p-benzoquinone gave stereoregular poly(arylene benzoquinonimines), close analogs of pernigraniline. The factors causing problems in achieving high yields and high molecular weight were identified. Reduction of the obtained polyquinonimines proceeded smoothly to the leucoemeraldine analogs, but no evidence for the formation of the electrically conductive emeraldine form was obtained.

  2. Articles

    1. Top of page
    2. Highlights
    3. Articles
    4. Notes
    1. Preparation of nanoparticles of double-hydrophilic PEO-PHEMA block copolymers by AGET ATRP in inverse miniemulsion (pages 4764–4772)

      Jung Kwon Oh,, Hongchen Dong, Rui Zhang, Krzysztof Matyjaszewski and Helmut Schlaad

      Version of Record online: 12 SEP 2007 | DOI: 10.1002/pola.22230

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      Stable nanoparticles based on well-controlled poly(2-hydroxyethyl methacrylate) (PHEMA) were prepared by atom transfer radical polymerization (ATRP) in inverse miniemulsion. The use of water-soluble mono- and difunctional poly(ethylene oxide)-based 2-bromoisobutyrate (PEO-Br) as a macroinitiator allowed for preparing well-defined PEO-PHEMA and PHEMA-PEO-PHEMA block copolymers with relatively high molecular weight (DP > 200) and low polydispersity (Mw/Mn < 1.3). These block copolymers self-assembled to form micellar nanoparticles being 10–20 nm in diameter, with uniform size distribution, and an aggregation number of ∼10. [Color version of the adjacent figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    2. Random fluorene copolymers with on-chain quinoxaline acceptor units (pages 4773–4785)

      Argiri Tsami, Xiao-Hui Yang, Frank Galbrecht, Tony Farrell, Hongbo Li, Sylwia Adamczyk, Ralf Heiderhoff, Ludwig Josef Balk, Dieter Neher and Elisabeth Holder

      Version of Record online: 12 SEP 2007 | DOI: 10.1002/pola.22231

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      Two series of random polyfluorene copolymers with on-chain benzo[g]quinoxaline or quinoxaline acceptor units were synthesized following a protocol according to Yamamoto resulting in novel copolymers that revealed blue to orange light emission in solution. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    3. Synthesis and optical properties of fluorene-based polymers incorporating organosilicon unit (pages 4786–4794)

      Koji Takagi, Hiroki Kakiuchi, Yasuo Yuki and Masato Suzuki

      Version of Record online: 10 MAR 2008 | DOI: 10.1002/pola.22210

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      Polymers with high molecular weight and good solubility could be obtained by Suzuki coupling polymerization from silylene-containing fluorene-based dibromo monomers and 9,9-dihexylfluorene-2,7-bis(trimethyleneborate). Three silylene-bridged polymers emitted pure-blue light both in solution and film. A polymer bearing tetraphenylsilole segment emitted green light in film due to the fluorescence resonance energy transfer.

    4. Surface interaction of well-defined, concentrated poly(2-hydroxyethyl methacrylate) brushes with proteins (pages 4795–4803)

      Chiaki Yoshikawa, Atsushi Goto, Yoshinobu Tsujii, Norio Ishizuka, Kazuki Nakanishi and Takeshi Fukuda

      Version of Record online: 14 SEP 2007 | DOI: 10.1002/pola.22224

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      A concentrated brush of poly(2-hydroxyethyl methacrylate) was chromatographically demonstrated to show excellent protein repellency due to a sharp size-exclusion effect with a low value of the critical molecular weight (size-exclusion limit); proteins larger than the distance between the nearest-neighbor graft points were perfectly excluded from the brush layer, suffering from little affinity interaction even at the outermost surface of the brush. These results present a new notion of biocompatibility.

    5. Fluorene-based liquid crystalline networks with linearly polarized blue emission (pages 4804–4817)

      Marta Millaruelo, Luiz S. Chinellato Jr., José Luis Serrano, Luis Oriol and Milagros Piñol

      Version of Record online: 14 SEP 2007 | DOI: 10.1002/pola.22225

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      Polarized blue-emitting films have produced by in- situ photopolymerization of liquid-crystalline mixture containing reactive nematic mesogens and fluorine-based emitting monomers. Influence of chemical structure of fluorine derivatives on the mesomorphic properties, dichroic properties, and photostability have been investigated.

    6. Synthesis of ABCD-type miktoarm star copolymers and transformation into zwitterionic star copolymers (pages 4818–4828)

      Xiaojun Wang, Junpo He and Yuliang Yang

      Version of Record online: 14 SEP 2007 | DOI: 10.1002/pola.22229

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      A facile one-pot method is reported to synthesize a novel well-defined ABCD-type 4-miktoarm star copolymer in which A denotes polystyrene (PS), B poly(tert-butyl methacrylate) (PtBuMA), C poly(α-methylstyrene) (PαMSt), and D poly(4-vinylpyridine) (P4VP), through m-DDPE route via anionic polymerization. The star polymer is hydrolyzed into zwitterionic equivalents, which was soluble at lower pH but insoluble in neutral and basic solution. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    7. Effect of introducing a cationic system into a thiol-ene photopolymerizable formulation (pages 4829–4843)

      Ricardo Acosta Ortiz, Bertha A. Puente Urbina, Liliana V. Cabello Valdez, Lydia Berlanga Duarte, Ramiro Guerrero Santos, Aída E. García Valdez and Mark D. Soucek

      Version of Record online: 17 SEP 2007 | DOI: 10.1002/pola.22234

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      When a hybrid formulation containing a thiol-ene system and an epoxide cationic curable system was irradiated with UV light, the thiol-ene component polymerized readily, but the cationic polymerization was inhibited by the sulfides obtained from the thiol-ene system. These sulfides can react with the oxonium terminated growing chains derived from the cationc polymerization to form trialkyl sulfonium salts. These salts can promote the polymerization of the remaining epoxide monomer in a post thermal treatment to produce hard and transparent hybrid polymers.

    8. Design and synthesis of a tribranched phenylethynyl-terminated aryl ether compound and its use as a reactive diluent for PETI-5 (pages 4844–4854)

      Xianhua Rao, Guodong Dang, Hongwei Zhou, Wei Yang, Gang Cui, Chunhai Chen and Rikio Yokota

      Version of Record online: 14 SEP 2007 | DOI: 10.1002/pola.22223

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      A novel tribranched, phenylethynyl-terminated aryl ether compound (Tri-PE-PAEK) was successfully synthesized. Its novel star-shaped, asymmetrical structure leads to a good combination of properties: a low melting temperature (252 °C) and good solubility in aprotic solvents, as well as a low melt viscosity (0.1 P at 280 °C). All these inherent advantages make it a promising diluent for phenylethynyl-terminated imide oligomer, which has the molecular weight of 5000 g/mol (PETI-5) to improve its processability. With only a 10% loading of Tri-PE-PAEK, the viscosity and the minimum temperature corresponding to the minimum viscosity are both remarkably reduced. Meanwhile, the toughness of a cured blended resin is greatly increased.

    9. Living cationic polymerization of vinyl ether with a cyclic acetal group (pages 4855–4866)

      Takeshi Namikoshi, Tamotsu Hashimoto and Michio Urushisaki

      Version of Record online: 14 SEP 2007 | DOI: 10.1002/pola.22235

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      The living cationic polymerization of 5-ethyl-2-methyl-5-(vinyloxymethyl)-1,3-dioxane (1), a vinyl ether with a cyclic acetal unit, was achieved with an isobutyl vinyl ether–acetic acid adduct/tin tetrabromide/2,6-di-tert-butylpyridine initiating system in toluene at 0 °C to give polymers (2) with relatively narrow molecular weight distributions (weight-average molecular weight/number-average molecular weight = 1.2–1.3). The thermal properties and acid-catalyzed hydrolysis of 2 (to obtain 3) were investigated.

    10. Synthesis and electroluminescent properties of a phenothiazine-based polymer for nondoped polymer light-emitting diodes with a stable orange-red emission (pages 4867–4878)

      Yingliang Liu, Huayu Cao, Jianghui Li, Zhijian Chen, Shaokui Cao, Lixin Xiao, Shengang Xu and Qihuang Gong

      Version of Record online: 14 SEP 2007 | DOI: 10.1002/pola.22237

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      A novel phenothiazine-based polymer was synthesized by a Heck reaction for nondoped polymer light-emitting diodes (PLEDs). The electroluminescent results suggested that the emission maximum was stabilized at 616 nm, and the coordinate value of Commission International de l'Eclairage 1931 was nearly stabilized at (x, y) = (0.62, 0.38). This indicated that nondoped PLEDs with the polymer as an active layer had a stable orange-red emission. The maximum luminance reached 2432 cd/m2. Additionally, the luminous efficiency of the double-layer PLEDs after the thermal treatment reached a balanceable state with an increase in the current, and this further proved the stable emission properties.

    11. Segmented sulfonated poly(arylene ether sulfone)-b-polyimide copolymers for proton exchange membrane fuel cells. I. Copolymer synthesis and fundamental properties (pages 4879–4890)

      Hae-Seung Lee, Anand S. Badami, Abhishek Roy and James E. McGrath

      Version of Record online: 14 SEP 2007 | DOI: 10.1002/pola.22238

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      Segmented disulfonated poly(arylene ether sulfone)-b-polyimide copolymers based on hydrophilic and hydrophobic oligomers were synthesized and evaluated for use as proton exchange membranes. The morphological characterization of the multiblock copolymers by AFM revealed that the multiblock copolymers had well-defined nano-phase separated morphologies which were clearly a function of block length. Hydrolytic stability tests at 80 °C water for 1000 h showed that multiblock copolymer membranes have much improved stability over polyimide random copolymers.

    12. Polymerization behaviors of racemic and chiral amphiphilic monomers in organized bilayer membranes of lamellar liquid crystalline phase (pages 4891–4900)

      Xinjiang Chen, Goh Matsuo, Bunsho Ohtani and Kaoru Tsujii

      Version of Record online: 14 SEP 2007 | DOI: 10.1002/pola.22240

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      Differences in polymerization rates of chiral and racemic amphiphilic monomers by using hydrophilic and hydrophobic initiators, proving the diffusion of initiators in the organized phase is another key factor which affects the polymerization behaviors greatly

    13. Synthesis of double silylene-bridged binuclear zirconium complexes and their use as catalysts for olefin polymerization (pages 4901–4913)

      Sheng Xu, Junji Jia and Jiling Huang

      Version of Record online: 18 SEP 2007 | DOI: 10.1002/pola.22241

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      A series of novel double silylene-bridged binuclear zirconium complexes [η5-RC5H4ZrCl2]2[μ, μ-(SiMe2)2(η5-C5H3)2] were synthesized by the reaction of (η5-RC5H4)ZrCl3·DME with [μ, μ-(SiMe2)2(η5-C5H3)2]Li2 in THF. and characterized by 1H-NMR, MS, IR, and EA. When activated with MAO, their all exhibited high activity for ethylene polymerization even under very low molar ratio of Al/Zr = 50 and PEs with broaden MWD was obtained.

    14. Photoinitiated curing of mono- and bifunctional epoxides by combination of active chain end and activated monomer cationic polymerization methods (pages 4914–4920)

      Marco Sangermano, Mehmet Atilla Tasdelen and Yusuf Yagci

      Version of Record online: 18 SEP 2007 | DOI: 10.1002/pola.22239

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      Photoinitiated cationic polymerization of mono- and bifunctional epoxy monomers, namely cyclohexeneoxide (CHO), 4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate (EEC), respectively by using sulphonium salts in the presence of hydroxylbutyl vinyl ether (HBVE) was studied. During the polymerization, HBVE has the ability to react via both active chain end (ACE) and activated monomer mechanisms through its hydroxyl and vinyl ether functionalities, respectively. Thus, more efficient curing was observed with the addition of HBVE into EEC containing formulations. It was also demonstrated that HBVE is effective in facilitating the photoinduced crosslinking of monofunctional epoxy monomer, CHO in the absence of a conventional crosslinker.

    15. Synthesis and characterization of wholly aromatic poly(azomethine)s containing donor–acceptor triphenylamine moieties (pages 4921–4932)

      Guey-Sheng Liou, Hung-Yi Lin, Yu-Lun Hsieh and Yi-Lung Yang

      Version of Record online: 18 SEP 2007 | DOI: 10.1002/pola.22228

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      N-(4-nitrophenyl)-4′,4″-bisformyl-diphenylamine was synthesized from N-(4-nitrophenyl)-diphenylamine by the Vilsmeier-Haack reaction. Soluble poly(azomethine)s (PAMs) were prepared by the solution polycondensation of N-(4-nitrophenyl)-4′,4″-bisformyl-diphenylamine and aromatic diamine in NMP at room temperature under reduced pressure. All the PAMs exhibited moderate high Tg values and thermal stability and showed highly soluble in various organic solvents, such as DMAc, chloroform, and THF. These PAMs in NMP solution showed UV-Vis CT absorptions at 405–421 nm and photoluminescence peaks around 462–466 nm. The HOMO and LUMO energy levels of these PAMs can be determined from cyclic voltammograms as 4.86–5.43 and 3.31–3.34 eV, respectively.

    16. Hydrazine-based polyimides from isomeric bis(chlorophthalimide)s (pages 4933–4940)

      Jingling Yan, Taihang Li, Zhen Wang, Lianxun Gao and Mengxian Ding

      Version of Record online: 18 SEP 2007 | DOI: 10.1002/pola.22201

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      The synthesis and properties of isomeric hydrazine-based polyimides were described in this paper. Isomeric dichloro-N, N′-biphthalimides (DCBPIs) were prepared from chlorophthalic anhydrides and hydrazine in acetic acid. Hydrazine-based polyimides were synthesized from isomeric DCBPIs and 4, 4′-thiobisbenzenethiol via the nucleophilic displacement reaction in DMAc. The isomeric effect on the properties of monomers and polymers was investigated and the results are as following: 3, 3′-DCBPI showed higher yield and better stability compared with 4, 4′-DCBPI; the orders of Tgs and hydrolytic stability of these isomeric polyimides were 3, 3′-DCBPI/TBBT > 3, 4′-DCBPI/TBBT > 4, 4′-DCBPI/TBBT.

    17. High-efficiency blue light-emitting polymers based on 3,6-silafluorene and 2,7-silafluorene (pages 4941–4949)

      Ergang Wang, Chun Li, Junbiao Peng and Yong Cao

      Version of Record online: 18 SEP 2007 | DOI: 10.1002/pola.22243

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      A novel blue-emitting polymer based on 3,6-silafluorene and 2,7-silafluorene shows high performance with an external quantum efficiency of 1.95%, a luminous efficiency of 1.69 cd A−1 and a maximal brightness of 6000 cd m−2 with the CIE coordinates of (0.162, 0.084).

    18. A density functional theory computational study of the role of ligand on the stability of CuI and CuII species associated with ATRP and SET-LRP (pages 4950–4964)

      Brad M. Rosen and Virgil Percec

      Version of Record online: 18 SEP 2007 | DOI: 10.1002/pola.22328

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      ATRP and SET-LRP both utilize Cu/N-ligand complexes to perform their activation and deactivation steps. DFT was used to determine the preferred ligand-binding geometries for Cu/N-ligand complexes. We find that those ligands capable of tetrahedral complexes with CuI and trigonal bipyramidal with axial halide complexes with [CuIIX]+ have higher energies of stabilization that correlate with increased propensity to disproportionate and with enhanced SET-LRP performance. By examining the relative energies of the basic steps of ATRP and SET-LRP, we were able to rationalize the transition from an ATRP to an SET-LRP mechanism as we transition from nonpolar to polar solvents. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    19. Synthesis and thermal crosslinking of oxazolidine-functionalized polyurethanes (pages 4965–4973)

      Robert Andreu, Gerard Lligadas, Joan Carles Ronda, Marina Galià and Virginia Cádiz

      Version of Record online: 18 SEP 2007 | DOI: 10.1002/pola.22336

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      A new oxazolidine derivative was obtained from phenol, 2-amino-2-methylpropane-1,3-diol, and paraformaldehyde. Linear segmented polyurethanes were prepared by reaction of different ratios of oxazolidine diol and commercial polyethylenglycol (Mw ca. 400) with 4,4′-methylenbis (cyclohexylisocyanate). The polyurethanes were thermally characterized and crosslinked by oxazolidine ring opening to obtain materials with improved thermal stability and with Tg between 30 and 140 °C, showing that these materials can be used as rubbers or rigid plastics.

    20. Synthesis, structural, and retrostructural analysis of helical dendronized poly(1-naphthylacetylene)s (pages 4974–4987)

      Virgil Percec, Jonathan G. Rudick, Mihai Peterca, Emad Aqad, Mohammad R. Imam and Paul A. Heiney

      Version of Record online: 18 SEP 2007 | DOI: 10.1002/pola.22265

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      Structural and retrostructural analysis of chiral, nonracemic (poly[(3,4,5)dm8G1-1EN]), and achiral (poly[(3,4,5) 12G1-1EN]) poly(1-naphthylacetylene)s demonstrated new design principles for helical dendronized polyarylacetylenes. Peripheral chiral tails select a preferred helical screw sense of the polyene backbone. In solution, the preferred helical conformation persists over a wide temperature range. In bulk, the naphthyl moiety facilitates a longer correlation length for helical order compared to an analogous minidendritic poly(phenylacetylene). [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    21. Influence of crystalline peripheral chain length on the solid-state assemblies of amphiphilic dendrons (pages 4988–4994)

      Yeon-Wook Chung, Byung-Ill Lee, Hyun-Yu Kim, Ulrich Wiesner and Byoung-Ki Cho

      Version of Record online: 18 SEP 2007 | DOI: 10.1002/pola.22287

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      Solid-state assemblies of amphiphilic dendrons, based on a third-generation aliphatic polyether dendritic core, can be modulated from lamellar to oblique columnar structures as a function of crystalline peripheral chain length. The observed assembly behavior can be explained by variation of dendron shape attributable to the degree of crystallization of alkyl peripheries. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    22. Nitroxide-mediated radical polymerization in miniemulsion: Bimolecular termination in monomer-free model systems (pages 4995–5004)

      Md. Nur Alam, Per B. Zetterlund and Masayoshi Okubo

      Version of Record online: 18 SEP 2007 | DOI: 10.1002/pola.22294

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      Bimolecular termination in nitroxide-mediated radical polymerization in miniemulsion has been investigated through heating a polystyrene–2,2,6,6-tetramethylpiperidinyl-1-oxy macroinitiator and its 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxy analogue in an aqueous toluene dispersion with sodium dodecyl benzenesulfonate as surfactant at 125 °C. The level of bimolecular termination by combination, evaluated from the high-molecular-weight shoulder, was higher in miniemulsion than in solution and increased with decreasing particle size. Quantitative analysis revealed that these results cannot be rationalized solely by nitroxide partitioning to the aqueous phase. The results are explained by an interface effect, by which nitroxide is adsorbed or located at the aqueous–organic interface. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    23. Preparation and properties of well-defined waterborne polyurethaneurea with fluorinated siloxane units in hard or soft segments (pages 5005–5016)

      Teng Su, Gui You Wang and Chun Pu Hu

      Version of Record online: 18 SEP 2007 | DOI: 10.1002/pola.22314

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      A model hard segment and soft segment containing fluorinated siloxane (PTFPMS), respectively, were synthesized first, from which two types of well-defined anionic polyurethaneurea (PUU) aqueous dispersions were prepared. The bulk as well as surface structure and properties of the PTFPMS-modified PUU could be adjusted by altering the sequence distribution of PTFPMS units along the macromolecular chains, hence their location in the hard or soft microdomain of PUU. This work presented an easy approach to achieve both the excellent waterproof performance and mechanical properties of the waterborne PUU.

  3. Notes

    1. Top of page
    2. Highlights
    3. Articles
    4. Notes
    1. You have free access to this content
      The influence of precursor's length and [diepoxide]o/[MPEG]o ratio on poly(ethylene glycol) star formation: The quantitative conversion of both precursors (pages 5017–5021)

      Grzegorz Lapienis

      Version of Record online: 18 SEP 2007 | DOI: 10.1002/pola.22332

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      The analysis of the relation between Mn of MPEG and [diepoxide]o/[MPEG]o ratio allowed to determine the demarcation line for conditions giving either soluble stars: DGNG (○) and DGEG (Δ) or insoluble products: DGNG (•) and DGEG (▴). Then conditions have been found for a quantitative conversion of both MPEG and diepoxides into stars. This was possible only for MPEG of Mn ≥ 2000. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    2. You have free access to this content
      Synthesis and association behavior of cationic amphiphilic copolymers consisting of quaternary ammonium and nonionic surfactant moieties (pages 5022–5030)

      Hiroshi Morikawa, Yotaro Morishima, Suguru Motokucho, Hisatoyo Morinaga, Haruo Nishida and Takeshi Endo

      Version of Record online: 18 SEP 2007 | DOI: 10.1002/pola.22322

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      Statistical copolymers of [2-(acryloxy)ethyl]trimethylammonium chloride and a surfactant macromonomer (surfmer) were synthesized by radical copolymerization, and their associative properties to form micelles in aqueous solution were characterized by fluorescence, 1H NMR, and dynamic light scattering techniques. Much lower critical micelle concentrations for the copolymers than those for the corresponding discrete surfactants were confirmed by a fluorescence analysis using a pyrene probe. Proton spin-lattice relaxation time (T1) for the copolymers in D2O indicated that the local motion of the dodecyl groups in hydrophobic microdomains formed by the polymer-bound surfactant moieties was not particularly restricted by main chains.

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