Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 44 Issue 19

1 October 2006

Volume 44, Issue 19

Pages 5445–5807

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      Ultrasound in polymer chemistry: Revival of an established technique (pages 5445–5453)

      Jos M. J. Paulusse and Rint P. Sijbesma

      Article first published online: 21 AUG 2006 | DOI: 10.1002/pola.21646

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      Ultrasound is evolving from a technique used to initiate polymerizations into a new method for synthetic chemistry. Ultrasound has been used to initiate polymerizations not only by degrading solvent molecules but also by breaking covalent polymers to form macroinitiators. Smart design has enabled researchers to cleave specific bonds in a polymer chain, and recently, ultrasound has also made its entry into coordination chemistry. Ultrasound can be used as a rheology switch, but completely new synthetic procedures have also been made possible. We describe here the development of ultrasound specifically in polymer chemistry, including its newest applications in reversible mechanochemistry.

  2. Articles

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    1. Controlling grafting density and side chain length in poly(n-butyl acrylate) by ATRP copolymerization of macromonomers (pages 5454–5467)

      Shigeki Ohno and Krzysztof Matyjaszewski

      Article first published online: 22 AUG 2006 | DOI: 10.1002/pola.21669

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      Two acryloyl-terminated poly(n-butyl acrylate) macromonomers with different degrees of polymerization (DPnBA = 25 and 42) prepared by ATRP were employed. “Grafting through” ATRP allowed for the synthesis of well-defined n-butyl acrylate graft polymers with different architecture. Tadpole-shaped and dumbbell-shaped graft polymers were successfully obtained by ATRP.

    2. Comprehensive study on the formation of polyelectrolyte complexes from (quaternized) poly[2-(dimethylamino)ethyl methacrylate] and poly(2-acrylamido-2-methylpropane sodium sulfonate) (pages 5468–5479)

      Dilyana Paneva, Laetitia Mespouille, Nevena Manolova, Philippe Degée, Iliya Rashkov and Philippe Dubois

      Article first published online: 21 AUG 2006 | DOI: 10.1002/pola.21594

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      The polyelectrolyte complex formation between well-defined (quaternized) poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) and high molecular weight poly(2-acrylamido-2-methylpropane sodium sulfonate) (PAMPSNa) paves the way to the preparation of a large range of adaptative macro-and nanosized polymer materials made of ammonium-based polycations and sodium sulfonate-based polyanions through the proper choice of tertiary amino groups (non- or quaternized ones).

    3. Synthesis and comparative solution properties of single-, twin-, and triple-tailed associating ionic polymers based on diallylammonium salts (pages 5480–5494)

      Sk. Asrof Ali, Yunusa Umar, B. F. Abu-Sharkh and Hasan A. Al-Muallem

      Article first published online: 21 AUG 2006 | DOI: 10.1002/pola.21624

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      The cycloterpolymerizations of three newly synthesized single-, twin-, and triple-tailed hydrophobic diallylammonium chlorides with hydrophilic monomer N,N-diallyl-N-car boethoxymethylammonium chloride and sulfur dioxide afforded a series of cationic polyelectrolytes, which upon the acidic hydrolysis of the pendent ester groups gave the corresponding pH-responsive cationic acid salts. The addition of NaOH converted the cationic acid salt samples to polybetaines, anionic polyelectrolytes, and polybetaine/anionic polyelectrolyte polymers containing various proportions of zwitterionic (polybetaine) and anionic fractions (anionic polyelectrolyte) in the polymer chain. The effects of the tail and charge types as well as the charge density on the polymer chain were investigated. The superior viscosity behavior of the polymers containing the triple-tailed hydrophobe was attributed to the blocky nature of the comonomer.

    4. New environmentally responsive fluorescent N-isopropylacrylamide copolymer and its application to DNA sensing (pages 5495–5504)

      Chang-Chung Yang, Yanqing Tian, Alex K.-Y. Jen and Wen-Chang Chen

      Article first published online: 22 AUG 2006 | DOI: 10.1002/pola.21629

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      Two novel multifunctional copolymers consist of a temperature-responsive poly(N-isopropylacrylamide) (PNIPAA) segment and a fluorescent fluorene-containing acrylic polymer segment with pH responsiveness and/or DNA-sensing ability were explored. The protonation of the amino moiety at a low pH improved the solubility and prevented aggregation for fluorescence quenching. However, the fluorene segment aggregated at room temperature under the basic condition due to its poor solubility in water, which was resolved above LCST by decreasing the microenvironmental polarity of PNIPAA segment. After the amino groups were quanternized, the obtained copolymer could be utilized as a biosensor for detecting DNA.

    5. Synthesis and characterization of a novel biodegradable, thermoplastic polyurethane elastomer (pages 5505–5512)

      Wenshou Wang, Peng Ping, Haijun Yu, Xuesi Chen and Xiabin Jing

      Article first published online: 21 AUG 2006 | DOI: 10.1002/pola.21643

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      A series of novel biodegradable, thermoplastic polyurethane elastomers were synthesized, with a random copolymer of L-lactide and ϵ-caprolactone used as the soft segment. They displayed excellent mechanical properties, such as a tensile strength as high as 38 MPa, a tensile modulus as low as 10 MPa, and an elongation at break of 1300%. Therefore, they could find applications in biomedical fields, such as soft-tissue engineering and artificial skin.

    6. Click chemistry in materials synthesis. II. Acid-swellable crosslinked polymers made by copper-catalyzed azide–alkyne cycloaddition (pages 5513–5518)

      Chunmei Li and M. G. Finn

      Article first published online: 21 AUG 2006 | DOI: 10.1002/pola.21623

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      A highly crosslinked hyperbranched polymer that rapidly swells and shrinks in a halogenated solvent in response to the addition of an acid or base has been prepared by Cu(I) catalysis of the reaction between a diazide and an amine-containing trialkyne. The triazole linkages in the polymer (circles in the image) are highly stable and may also play a role in the swelling behavior. The swelling–deswelling process is reversible.

    7. Infrared thermography analysis of the thermally latent polymerization of 3-ethyl-3-phenoxymethyloxetane (pages 5519–5524)

      Tomomi Nagasawa, Bungo Ochiai and Takeshi Endo

      Article first published online: 21 AUG 2006 | DOI: 10.1002/pola.21641

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      Temperature changes during the thermally latent polymerization of 3-ethyl-3-phenoxymethyloxetane were analyzed by infrared thermography to attain fast screening of multiple samples. The temperature changes in the polymerization depended on the polymerization rates. That is, a fast polymerization was exothermic, increasing the temporal temperature of the polymerization by approximately 130 °C within a few minutes.

    8. Cyclocopolymerization of 1,4-pentadiene with ethene in the presence of group-4 metallocenes (pages 5525–5532)

      Mariagrazia Napoli, Chiara Costabile, Gabriella Cavallo and Pasquale Longo

      Article first published online: 22 AUG 2006 | DOI: 10.1002/pola.21647

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      rac-[CH2(3-tert-butyl-1-indenyl)2]ZrCl2 activated by methylaluminoxane in ethene/1,4-pentadiene copolymerization produces inserted methylene-1,3-cyclobutane units and a large number of crosslinks.

    9. Synthesis and characterization of a helical step-ladder polyarylene (pages 5533–5545)

      Benjamin S. Nehls, Frank Galbrecht, David J. Brauer, Christian W. Lehmann, Ullrich Scherf and Tony Farrell

      Article first published online: 21 AUG 2006 | DOI: 10.1002/pola.21552

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      A helical step-ladder polyarylene incorporating chiral (R)-2,2′-dioctyloxy-1,1′-binaphthyl units was synthesized for the first time. The synthetic strategy comprised a microwave-assisted Suzuki cross-coupling followed by Friedel–Crafts-type, polymer-analog, intramolecular cyclization. Related bis(naphthyl)benzene model compounds were prepared in a similar fashion, and this was followed by a comparative examination of the NMR and ultraviolet–visible data. The optical spectra showed only a very weak interaction across the binaphthyl units. The circular dichroism spectrum of the helical step-ladder polymer exhibited a strong bisignate Cotton effect in the π–π* absorption region, which indicated strong exciton coupling within the helical polymer chain.

    10. Multicyclic polyethers by the polycondensation of 1,2- or 1,3-dicyanotetrafluorobenzene with flexible diphenols (pages 5546–5556)

      Hans R. Kricheldorf, Johann Schellenberg and Gert Schwarz

      Article first published online: 21 AUG 2006 | DOI: 10.1002/pola.21675

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      Polycondensations of flexible diphenols with tetrafluorophthalodinitrile in a feed ratio of 2:1 yielded multicyclic polyethers that, upon heating with metal ions, yielded crosslinked phthalocyanines. Isomeric tetrafluoroisophthalodinitrile reacted in a different way.

    11. Synthesis and investigation of the effect of nematic phases on the glass-transition behavior of novel cycloaliphatic liquid-crystalline poly(ester amide)s (pages 5557–5571)

      P. Deepa, C. Sona and M. Jayakannan

      Article first published online: 23 AUG 2006 | DOI: 10.1002/pola.21677

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      We demonstrate a new method for introducing nematic, liquid-crystalline (LC) phases into commercially important cycloaliphatic polyesters such as poly(1,4-cyclohexanedimethylene terephthalate). The introduction of nematic LC phases drastically affects the glass transition, regardless of the structural differences of the amide units, and the copolymers deviate from the Flory–Fox trend. A plot of the composition versus the glass-transition temperature passes through a maximum at a lower amide composition because of the cooperative effect of the strong alignment of polymer chains in the nematic phases and intermolecular packing arising from the hydrogen-bonding interactions in the poly(ester amide)s.

    12. Exfoliation of montmorillonite by the insertion of disklike micelles via the soap-free emulsion polymerization of methyl methacrylate (pages 5572–5579)

      King-Fu Lin, Shanq-Chyang Lin, An-Ting Chien, Chi-Chun Hsieh, Ming-Huei Yen, Chia-Hsin Lee, Chao-Sung Lin, Wen-Yen Chiu and Yuan-Hon Lee

      Article first published online: 21 AUG 2006 | DOI: 10.1002/pola.21657

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      The exfoliation of montmorillonite nanosheets by growing disklike micelles during the soap-free emulsion polymerization of methyl methacrylate, which were apparently inserted into the interlayer region of montmorillonite, is shown.

    13. Flame retardant epoxy resins based on diglycidyloxymethylphenylsilane (pages 5580–5587)

      L. A. Mercado, J. A. Reina and M. Galià

      Article first published online: 23 AUG 2006 | DOI: 10.1002/pola.21673

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      Silicon-containing epoxy resins were prepared from diglycidyloxymethylphenyl silane (DGMPS) and diglycidylether of bisphenol A (DGEBA) by crosslinking with 4,4′-diaminodiphenylmethane. Several DGMPS/DGEBA molar ratios were used to obtain materials with different silicon content. The weight loss rate of the silicon-containing resins is lower than that of the silicon free resin and char yields under nitrogen and air atmospheres increase with the silicon content. The presence of silicon increases the LOI values to 36.0.

    14. Exploring 9-arylcarbazole moiety as the building block for the synthesis of photoluminescent group 10–12 heavy metal diynes and polyynes with high-energy triplet states (pages 5588–5607)

      Li Liu, Wai-Yeung Wong, Jian-Xin Shi and Kok-Wai Cheah

      Article first published online: 23 AUG 2006 | DOI: 10.1002/pola.21666

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      A new series of metal diynes and polyynes of group 10–12 transition elements containing various p-substituted 9-phenylcarbazole moieties are prepared and optically characterized. The heavy-atom perturbation of Pt(II), Au(I), and Hg(II) ions in triplet-light-harvesting and the influence of the 9-aryl moiety of carbazole on the phosphorescent properties of these metal-organic materials are examined.

    15. Switchable thin-film surface prepared via a simple grafting-to method using a polystyrene-b-poly(2-vinylpyridine) copolymer (pages 5608–5617)

      Ying Wang, Joseph X. Zheng, William J. Brittain and Stephen Z. D. Cheng

      Article first published online: 23 AUG 2006 | DOI: 10.1002/pola.21692

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      A polystyrene-b-poly(2-vinylpyridine) block copolymer containing a methylhydridosilane linking group was chemically grafted to an 8-trichlorosilyloctene monolayer via a simple one-step hydrosilylation reaction. The resulting Y-shaped thin film exhibited a low grafting density, which was characteristic of the grafting-to technique. To further reduce the miscibility of the two arms, methyl iodide was reacted with the poly(2-vinylpyridine) block to produce quaternary ammonium groups. The surfaces before and after quaternization were both solvent-switchable when subjected to block-selective solvents.

    16. Free-radical copolymerization of ethyl α-hydroxymethylacrylate with methyl methacrylate by reversible addition–fragmentation chain transfer (pages 5618–5629)

      R. Cuervo-Rodríguez, V. Bordegé, M. Sánchez-Chaves and M. Fernández-García

      Article first published online: 23 AUG 2006 | DOI: 10.1002/pola.21702

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      Ethyl α-hydroxymethylacrylate derived polymers were synthesized by a reverse addition–fragmentation process. The reactions presented linear kinetics until the value at which deceleration occurred. This conversion limit decreased when the fraction of ethyl α-hydroxymethylacrylate in the feed increased. The polymers presented molecular weights similar to those predicted and reasonably low polydispersity indices.

    17. Synthesis and properties of thermosetting polymers from a phosphorous-containing fatty acid derivative (pages 5630–5644)

      G. Lligadas, J. C. Ronda, M. Galià and V. Cádiz

      Article first published online: 23 AUG 2006 | DOI: 10.1002/pola.21691

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      A new phosphorous-containing fatty acid diepoxide was ob tained from 10-undecenoyl chloride and 10-(2′,5′-dihydroxy phenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- oxide and crosslinked with 4,4′-diaminodiphenylmethane (DDM) and bis(m-aminophenyl) methylphosphine oxide (BAMPO). The properties of the thermosetting materials were evaluated by DSC, DMTA, TGA, and LOI. Thermal and thermooxidative degradation was studied by GC/MS, FTIR, 31P MAS NMR spectroscopy and SEM. LOI values indicate good flame retardant properties.

    18. Polyketanils. Polymers protonated with Bronsted acid (pages 5645–5660)

      Agnieszka Iwan, Bozena Kaczmarczyk, Janusz Kasperczyk, Jan Jurusik, Henryk Janeczek, Danuta Sek and Zbigniew mazurak

      Article first published online: 23 AUG 2006 | DOI: 10.1002/pola.21705

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      New luminescent materials—aromatic polyketanils (PKs) were synthesized with the goal of studying the interactions between the polymer chains, primary dopant [1,2-(di-2-ethylhexyl)ester of 4-sulfophthalic acid (PSA)], and secondary dopant [m-cresol (MC)] with NMR, FTIR, ultraviolet–visible, and photoluminescence measurements. Spectral changes were observed for the PKs after primary and secondary doping, and they supported ionic- and hydrogen-bond formation between the PKs and the PSA and MC, respectively.

    19. α,α-Dibromotoluene as a monomer for poly (substituted methylene) synthesis: Magnesium-mediated polycondensation of α,α-dibromotoluene and magnesium/copper-mediated copolycondensation of α,α-dibromotoluene with 1,6-dibromohexane (pages 5661–5671)

      Eiji Ihara, Takao Wake, Naoki Mokume, Tomomichi Itoh and Kenzo Inoue

      Article first published online: 23 AUG 2006 | DOI: 10.1002/pola.21637

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      α,α-Dibromotoluene 1 was found to be polymerized by the reaction with excess Mg to give poly(phenylmethylene)s 2, whose main chains were partially dehydrogenated to carbon–carbon double bonds (C[DOUBLE BOND]C). The C[DOUBLE BOND]Cs in 2 can be brominated by treatment with Br2. The polymerization mechanism was presumed to include the formation of Grignard reagents of various species with benzylic C[BOND]Br bonds and the nucleophilic attacks of the Grignard reagents to various compounds with benzylic C[BOND]Br bonds. Copolymerization of 1 with dichlorodimethylsilane successfully proceeded. Mg/Cu-mediated copolycondensation of 1 with 1,6-dibromohexane 15 proceeded to give polymers that have similar compositions to those of random copolymers of ethylene and styrene.

    20. Synthesis and characterization of a new disubstituted polyacetylene containing indolylazo moieties in side chains (pages 5672–5681)

      Zhen Li, Qianqian Li, Anjun Qin, Yongqiang Dong, Jacky W. Y. Lam, Yuping Dong, Cheng Ye, Jingui Qin and Ben Zhong Tang

      Article first published online: 23 AUG 2006 | DOI: 10.1002/pola.21638

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      The first example of a disubstituted polyacetylene containing indolylazo moieties in its side chains was prepared by a post-functionalization strategy. The polymer shows good transparency and moderate macroscopic second-order optical nonlinearity. Its nonlinear optical activity (d33) is stable at a temperature as high as ∼150 °C.

    21. Effect of excess halide on the palladium-catalyzed insertion-triggered radical copolymerization of methyl acrylate and 1-hexene (pages 5682–5691)

      Ana C. Albéniz, Pablo Espinet and Raquel López-Fernández

      Article first published online: 23 AUG 2006 | DOI: 10.1002/pola.21634

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      The addition of chloride to neutral palladium pentafluorophenyl complexes led to an active catalyst system for the radical copolymerization of methyl acrylate and 1-hexene with moderate yields. Anionic alkyl derivatives are formed at the beginning of the reaction, and homolytic cleavage of the Pd[BOND]C bond in these derivatives is easier than in the neutral analogues, ensuring the generation of radicals active in the polymerization process.

    22. Synthesis, characterization, and electrical properties of a diazodiphenylene-bridged Cu–phthalocyanine polymer (pages 5692–5698)

      Cemil Alkan, Leyla Aras and Güngör Gündüz

      Article first published online: 23 AUG 2006 | DOI: 10.1002/pola.21554

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      A diazodiphenylene-bridged Cu phthalocyanine polymer was synthesized by the condensation of the diazonium salt of diaminodiphenylene with the Cu(II) 1,8,15,22-tetraaminophthalocyanine complex and characterized. The polymer's electrical conductivity was studied with a four-prop system, and it was increased by 104 magnitudes via doping with iodine and hydrogen chloride. The diazodiphenylene-bridged Cu–phthalocyanine polymer was found to be an electroactive material by an investigation of the cyclic voltammetry.

    23. ABC-type hetero-arm star terpolymers through “Click” chemistry (pages 5699–5707)

      Ozcan Altintas, Gurkan Hizal and Umit Tunca

      Article first published online: 23 AUG 2006 | DOI: 10.1002/pola.21633

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      Hetero arm star ABC type terpolymers, poly(methyl meth acrylate)-polystyrene-poly(tert-butyl acrylate) (PMMA-PS-PtBA) and PMMA-PS-poly(ethylene glycol) (PEG) were prepared via “Click” chemistry strategy. For this aim, firstly, well-defined polymers, PMMA-b-PS with alkyne functional group at the junction point was obtained from combination of atom transfer radical polymerization (ATRP)/nitroxide-mediated radical polymerization (NMP) routes. Moreover, PtBA obtained from ATRP of tBA and commercially available mono hydroxyl PEG were easily converted to azide end-functionalized polymers. Next, alkyne and azide functional polymers were reacted in order to give hetero arm star polymers in the presence of CuBr/N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA) in DMF at room temperature for 24 h.

    24. Reversible-addition fragmentation chain transfer radical emulsion polymerization by a nanoprecipitation process (pages 5708–5718)

      Andrea R. Szkurhan, Takahito Kasahara and Michael K. Georges

      Article first published online: 23 AUG 2006 | DOI: 10.1002/pola.21635

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      A newly developed nanoprecipitation technique used for the formation of particles, originally applied to the nitroxide-mediated stable free radical polymerization process to enable emulsion polymerizations to proceed under living-radical polymerization conditions, has been extended to the reversible-addition fragmentation chain transfer (RAFT) system. The nanoprecipitation technique consists of precipitating an acetone solution of a macroRAFT reagent into a solution of poly(vinyl alcohol) in water to form polymer particles. The particles are swollen with monomer and heated under an inert atmosphere. Styrene emulsion polymerizations were studied at 65 °C and 75 °C in which either potassium persulfate, benzoyl peroxide, or a combination of both was used as an initiating source. However, the highest conversions were obtained when the polymerizations were conducted at 105 °C, in which case the autoinitiation of styrene was the initiating source. Plots of number average molecular weight versus conversion were linear indicating a controlled polymerization. The resulting latexes were colloidally stable and gave particle size distributions with a typical average particle diameter of 140 nm.

    25. Synthesis of poly(n-hexyl isocyanate-b-N-vinylpyrrolidone) block copolymers by the combination of anionic and nitroxide-mediated radical polymerizations: Micellization properties in aqueous solutions (pages 5719–5728)

      Panayiotis Bilalis, Georgia Zorba, Marinos Pitsikalis and Nikos Hadjichristidis

      Article first published online: 23 AUG 2006 | DOI: 10.1002/pola.21676

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      A double-headed initiator was employed for the synthesis of poly(n-hexyl isocyanate-b-N-vinylpyrrolidone) (PHIC-b-PNVP) block copolymers by a combination of anionic and nitroxide-mediated radical polymerizations. The micellar properties of the PHIC-b-PNVP block copolymers were studied in water, which was a selective solvent for the poly(N-vinylpyrrolidone) blocks.

    26. Synthesis and characterization of novel hyperbranched polybenzimidazoles based on an AB2 monomer containing four amino groups and one carboxylic group (pages 5729–5739)

      Z. X. Li, J. H. Liu, S. Y. Yang, S. H. Huang, J. D. Lu and J. L. Pu

      Article first published online: 23 AUG 2006 | DOI: 10.1002/pola.21668

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      A new AB2 monomer, 4-[2,6-bis(3,4-diaminophenyl)pyridin-4-yl]benzoic acid (BPBA), was synthesized, and aromatic hyperbranched polybenzimidazoles (HPBIs) were prepared through the self-polymerization of BPBA and functionalized with aromatic acids. The polymers had a high degree of branching (0.68) and medium molecular weights. The HPBIs had good solubility in strongly aprotic solvents. They also exhibited excellent thermal properties, with glass-transition temperatures of 318–381 °C and 10% weight loss in the range of 338–674 °C in nitrogen and 329–509 °C in air.

    27. Multiarm star nanocarriers containing a poly(ethylene imine) core and polylactide arms (pages 5740–5749)

      M. Adeli and R. Haag

      Article first published online: 23 AUG 2006 | DOI: 10.1002/pola.21664

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      This article explains the synthesis and application of star dendritic supramolecules containing a poly(ethylene imine) core and poly(lactide) arms for the transportation of some of small guest molecules.

    28. Coumarin-containing poly(fluorenediylvinylene)s: Synthesis, photophysics, and electroluminescence (pages 5750–5762)

      Vasilis P. Barberis, John A. Mikroyannidis and Věra Cimrová

      Article first published online: 25 AUG 2006 | DOI: 10.1002/pola.21655

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      Two soluble poly(fluorenevinylene)s (CV and CF), bearing aliphatic side chains terminated with coumarin, were synthesized via Heck coupling. CV and CF thin films emitted bluish-green and orange light with photoluminescence maxima at 475 and 585 nm, respectively. Single-layer light-emitting devices with an indium tin oxide/polymer/aluminum configuration showed green and orange electroluminescence with external efficiencies of 0.02 and 0.06% for CV and CF, respectively.

    29. Kinetics of the iodine transfer polymerization of vinylidene fluoride (pages 5763–5777)

      Cyrille Boyer, David Valade, Patrick Lacroix-Desmazes, Bruno Ameduri and Bernard Boutevin

      Article first published online: 30 AUG 2006 | DOI: 10.1002/pola.21654

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      The variation of the number-average degree of polymerization (DPn) versus the monomer conversion is shown for the iodine transfer polymerization of vinylidene fluoride (VDF) performed with different chain-transfer agents (1-iodo-2H,2H-perfluoro-octane (▪) and 1,1,2,2-tetrafluoro-3-iodopropane (▴)) at 75 °C.

    30. Cationic, water-soluble, fluorene-containing poly(arylene ethynylene)s: Effects of water solubility on aggregation, photoluminescence efficiency, and amplified fluorescence quenching in aqueous solutions (pages 5778–5794)

      Yan-Qin Huang, Qu-Li Fan, Xiao-Mei Lu, Chun Fang, Shu-Juan Liu, Li-Hui Yu-Wen, Lian-Hui Wang and Wei Huang

      Article first published online: 25 AUG 2006 | DOI: 10.1002/pola.21628

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      Three cationic water-soluble fluorene-containing poly(arylene ethynylene)s (P1′P3′) were synthesized. On the basis of studies on the photophysical properties, modulating the water solubility of these polymers was demonstrated to be an effective way of modulating their degrees of aggregation in water. The water solubility was gradually improved from P3′ to P1′ with increasing contents of ammonium-functionalized side chains. With the reduction of the water solubility from P1′ to P3′, they exhibited a gradually increased degree of aggregation in water. P1′ presented minimal aggregation, whereas P2′ and P3′ exhibited relatively disordered aggregation rather than the more ordered cofacial aggregation displayed by previously reported water-soluble PPE–SO3.

  3. Rapid Communications

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    2. Highlight
    3. Articles
    4. Rapid Communications
    1. You have free access to this content
      Fast living cationic polymerization of vinyl ethers with iron(III) chloride in the presence of a cyclic ether: Most active and environmentally benign catalyst for the living cationic polymerization of vinyl ethers (pages 5795–5800)

      Arihiro Kanazawa, Yumi Hirabaru, Shokyoku Kanaoka and Sadahito Aoshima

      Article first published online: 25 AUG 2006 | DOI: 10.1002/pola.21632

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      The fast living cationic polymerization of isobutyl vinyl ether was demonstrated with FeCl3 as a Lewis acid catalyst in the presence of a cyclic ether. The reaction was completed in 15 s even under mild conditions and was 5 or 1000 times faster than the reaction with SnCl4 or EtAlCl2, respectively, in the presence of 1,4-dioxane. The faster reaction was attributed to the superior ability of FeCl3 to extract Cl in comparison with the other two acids. In addition, the molecular weight distributions of the product polymers were invariably very narrow (weight-average molecular weight/number-average molecular weight < 1.1). Through the reduction of the basicity of a cyclic ether (e.g., 1,3-dioxolane), ultrafast living polymerization (97% in 3 s) was achieved.

    2. You have free access to this content
      Effects of ionic interactions between clay and waterborne polyurethanes on the structure and physical properties of their nanocomposite dispersions (pages 5801–5807)

      Hsun-Tsing Lee, Jiunn-Jer Hwang and Hsin-Jiant Liu

      Article first published online: 25 AUG 2006 | DOI: 10.1002/pola.21663

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      A waterborne polyurethane (WPU)/clay dispersion is electrostatically stabilized by [BOND]COO ions of WPU. Meanwhile, a stable electrical double layer is formed around each WPU/clay particle. The cations of clay platelets interact with [BOND]COO ions and interfere with the double layer of a pristine WPU dispersion. The WPU/clay dispersion, disturbed by ionic clay platelets, has fewer effective hydrophilic groups for stabilization in water. This leads to a larger particle size. Moreover, a WPU/clay dispersion with a higher clay concentration exhibits a higher viscosity. This is due to the stronger electrostatic interactions among a larger quantity of clay ions.

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