Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 42 Issue 12

15 June 2004

Volume 42, Issue 12

Pages 2845–3090

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      Organic and polymer chemistry of electrophilic tri- and tetrasubstituted ethylenes (pages 2845–2858)

      H. K. Hall Jr. and Anne Buyle Padias

      Article first published online: 30 APR 2004 | DOI: 10.1002/pola.20190

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      A survey of the spontaneous reactions of electrophilic olefins and nucleophilic olefins is presented as an area in which organic chemistry merges with polymer chemistry. The products include both small molecules and polymers, arising via tetramethylene biradical zwitterions that can cyclize or initiate polymerizations.

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    1. Abilities of 1-(9-anthrylmethyloxy)-2-pyridone and related compounds to initiate radical and cationic photopolymerizations (pages 2859–2865)

      Kenta Tanaka, Kanako Nakamura, Nariyoshi Yoshioka, Atsushi Kameyama, Tetsutaro Igarashi and Tadamitsu Sakurai

      Article first published online: 3 MAY 2004 | DOI: 10.1002/pola.20090

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      This study explored the abilities of 1-(9-anthrylmethyloxy)-2-pyridone and related compounds, which absorb long-wavelength light (>350 nm), to photochemically initiate radical and cationic polymerizations. It was found that the irradiation of the title compounds initiates the radical polymerization of styrene whereas the cationic polymerization of oxetane proceeds in the presence of these photoinitiators to a negligible extent. The behavior of 9-anthrylmethyloxyl and amidyl radicals in the photopolymerization process of styrene was discussed based on 1H NMR, UV, and fluorescence spectral data. In addition, the photoinitiation ability of the anthrylmethyloxyl end group was also investigated by using its model compound.

    2. Sulfonated poly(aryl ether ketone)s containing naphthalene moieties obtained by direct copolymerization as novel polymers for proton exchange membranes (pages 2866–2876)

      Peixiang Xing, Gilles P. Robertson, Michael D. Guiver, Serguei D. Mikhailenko and Serge Kaliaguine

      Article first published online: 3 MAY 2004 | DOI: 10.1002/pola.20152

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      Novel sulfonated poly(aryl ether ketone)s (SPAEK)s were prepared by aromatic nucleophilic polycondensation of 2,6-dihydroxynaphthalene with 5,5′-carbonyl-bis-(2-fluorobenzenesulfonate) and 4,4′-difluorobenzophenone. The dependence of the water uptake, swelling, and proton conductivity of the tough and flexible membranes on the degree sulfonation at different temperatures was studied. SPAEK membranes with DS from 0.72 to 1.60 not only maintained adequate mechanical properties after immersion in hot water, but also showed high proton conductivity, well above 1 × 10−2 S/cm at 80°C.

    3. New approaches for the synthesis of hindered C60-containing polyphosphazenes via functionalized intermediates (pages 2877–2885)

      Zhen Li, Jingui Qin and Xiaojuan Xu

      Article first published online: 5 MAY 2004 | DOI: 10.1002/pola.20147

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      Two new functional polyphosphazene intermediates, polyphosphazene with azide side groups and polyphosphazene with end amino groups, were prepared from poly(dichlorophosphazene) through a series of postfunctional reactions. These two intermediates are stable in air. In this study the new intermediates were successfully applied to the synthesis of C60-containing polyphosphazenes. It is believed that other functional polyphosphazenes also could be prepared by these two new intermediates.

    4. Synthesis and characterization of an azobenzene- and acrylamide-based photoresponsive copolymer and gel (pages 2886–2896)

      M. Moniruzzaman, G. F. Fernando and J. D. R. Talbot

      Article first published online: 5 MAY 2004 | DOI: 10.1002/pola.20108

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      A photoresponsive copolymer and its hydrogel were synthesized on the basis of acrylamide and azobenzene functionality. The copolymer and gel were fully characterized and consisted of a chemically joined material. Physicochemical properties such as the solubility in various solvents and the isomerisation rate of the azobenzene trans–cis entity were determined. The important gels as potential photoactuators were due to the large volume change they underwent in water (swelling) and the influence that photoisomerizable groups may have played in this. Accordingly, the swelling–unswelling behavior of the synthesized gel in water was investigated, and the diffusion coefficient of water in the gel was variable. This implies that the mechanism for predicting volume changes of such photoresponsive hydrogels may be complex.

    5. Synthesis and properties of novel conjugated poly(silylacetylene silazane)s (pages 2897–2903)

      Ji Dong Hu, Zhi Min Zheng, Teng Ma, Zhi Jie Zhang, Jian Ping Ye, Duo Yuan Wang and Ze Min Xie

      Article first published online: 5 MAY 2004 | DOI: 10.1002/pola.20155

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      A series of novel conjugated polymers, poly(silylacetylene silazane)s with different substituents were prepared by ammonolysis of corresponding α,ω-dichlorosilyleneacetylene oligomers. Differences were observed in the properties of the resulting polymers containing three different structures. The resulting polymers had good thermal properties and they showed moderately fluorescent. Their thermal stability was improved and obvious red-shift was observed when phenyl substituent was attached on silicon atom of polymers in emission spectra. The influence of concentrations and solvents on optical property of these polymers was also investigated in this article.

    6. Synthesis of graft copolymer from copolymerization of styrene-terminated poly(ethylene oxide) macromonomer and styrene with CpTiCl3/methylaluminoxane catalyst (pages 2904–2910)

      Kiyoshi Endo and Tomoaki Sugita

      Article first published online: 5 MAY 2004 | DOI: 10.1002/pola.20087

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      Copolymerization of styrene (St) and St-terminated poly(ethylene oxide) macromonomer (SEOM) with CpTiCl3/methylaluminoxane catalyst in toluene was investigated. The copolymerization of St and SEOM proceeded easily to give a graft copolymer consisting of syndiotactic polystyrene as the main chain and hydrophilic poly(ethylene oxide) as the side chain. The reactivity of SEOM depended on it molecular weight. The thermal properties of the graft copolymer such as the melting temperature were influenced by the introduction of SEOM.

    7. Synthesis and characterization of alt-bipyridinylene-phenylene copolymers containing ruthenium(II) complexes (pages 2911–2919)

      Thomas Pautzsch and Elisabeth Klemm

      Article first published online: 7 MAY 2004 | DOI: 10.1002/pola.20025

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      A series of alt-bipyridinylene-phenylene copolymers containing ruthenium(II) complexes were synthesized by the Suzuki coupling reaction. The alternating structure of the copolymers was confirmed by 1H and 13C NMR and elemental analysis. The polymers showed, by ultraviolet–visible, the π–π* absorption of the polymer backbone (320–380 nm) and at a lower energy attributed to the d–π* metal-to-ligand charge-transfer absorption (450 nm for linear 3a and 480 nm for angular 3b). The polymers were characterized by a monomodal molecular weight distribution. The degree of polymerization was approximately 8 for polymer 3b and 28 for polymer 3d.

    8. Synthesis of polybutadiene-graft-poly(dimethylsiloxane) and polyethylene-graft-poly(dimethylsiloxane) copolymers with hydrosilylation reactions (pages 2920–2930)

      A. E. Ciolino, O. I. Pieroni, B. M. Vuano, M. A. Villar and E. M. Vallés

      Article first published online: 7 MAY 2004 | DOI: 10.1002/pola.20032

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      Polybutadiene-graft-poly(dimethylsiloxane) copolymers were synthesized by hydrosilylation reactions between commercial polybutadiene and ω-silane poly(dimethylsiloxane) catalyzed by cis-dichloro bis(diethylsufide) platinum(II) salt. By subsequent hydrogenation of these copolymers, polyethylene-graft-poly(dimethylsiloxane) copolymers were obtained. The chemical compositions of these copolymers were determined by 1H and 13C NMR spectroscopies.

    9. Atom-transfer radical grafting polymerization of 2-methacryloyloxyethyl phosphorylcholine from silicon wafer surfaces (pages 2931–2942)

      Wei Feng, John Brash and Shiping Zhu

      Article first published online: 7 MAY 2004 | DOI: 10.1002/pola.20095

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      2-Methacryloyloxyethyl phosphorylcholine (MPC), a biomimetic monomer, was grafted from silicon wafer surfaces at room temperature by combining self-assembly of initiator and surface-initiated atom transfer radical polymerization. The surface thickness increased linearly with MPC conversion. Poly(MPC) layers of >100 nm thick were obtained by optimizing the polymerization conditions. A second block of either poly(MPC) or poly[2-(dimethylamino)ethyl methacrylate] was grown from the grafted poly(MPC), demonstrating the system livingness.

    10. New class of cationic ring-opening polymerizations of 2,2-diphenyl-1,3-oxathiolanes accompanying quantitative elimination of benzophenone (pages 2943–2949)

      Osamu Haba, Nobuaki Sasaki, Yusuke Sasaki and Takeshi Endo

      Article first published online: 7 MAY 2004 | DOI: 10.1002/pola.20086

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      Cationic polymerizations of 2-substituted 1,3-oxathiolanes 1a1c were carried out with boron trifluoride etherate (BF3 · OEt2) in dichloromethane at 30 °C to obtain poly(alkylene sulfide)s accompanying the elimination of benzophenone. In the cationic polymerization of 1b and 1c, the consumption of the monomers and formation of benzophenone proceeded simultaneously. The obtained poly(propylene sulfide)s from 1b and 1c contain 41% head–head units, which is in good agreement with that of the polymer from methylthiirane with BF3 · OEt2.

    11. Synthesis of pH-sensitive surfactants by the terpolymerization of methacrylic acid, methoxy poly(ethylene glycol) methacrylate, and lauryl methacrylate: Initiator effect and reactivity ratio study (pages 2950–2959)

      A. Sabrina Restrepo, Neissa M. Pinzón and Lu-Kwang Ju

      Article first published online: 10 MAY 2004 | DOI: 10.1002/pola.20105

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      For application in water-in-oil fermentation, pH-sensitive surfactants were synthesized by free-radical terpolymerization of methacrylic acid (MAA), methoxy poly(ethylene glycol) methacrylate (MPEGMA), and lauryl methacrylate (LMA). Two initiators, azobisisobutyronitrile (AIBN) and hydrogen peroxide, were studied. AIBN at 0.45% was the best, giving similar conversions of all three monomers. The subsequent study indicated that MPEGMA caused an increase-then-decrease profile of MAA conversion, fairly consistent with the well-known type II template polymerization of poly(ethylene glycol) (PEG)–MAA systems. The obtained reactivity ratios suggested a polymer structure of alternating blocks of MAA and LMA, with isolated PEG grafts.

    12. Living cationic polymerization of vinyl ethers with a urethane group (pages 2960–2972)

      Takeshi Namikoshi, Tamotsu Hashimoto and Toshiyuki Kodaira

      Article first published online: 10 MAY 2004 | DOI: 10.1002/pola.20145

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      To study the possibility of living cationic polymerization of vinyl ethers with a urethane group, 4-vinyloxybutyl n-butylcarbamate (1) and 4-vinyloxybutyl phenylcarbamate (2) were polymerized with the hydrogen chloride/zinc chloride initiating system in methylene chloride solvent at −30 °C. The polymerization of 1 was very slow and gave only low-molecular-weight polymers with anumber-average molecular weight (Mn) of about 2000 even at 100% monomer conversion. In contrast, the polymerization of vinyl ether 2 proceeded much faster than that of 1 and led to living polymerization to give high-molecular-weight polymers (Mn = ∼20,000) with narrow molecular weight distributions (≤∼1.2).

    13. Side-chain functionalized polymers containing bipyridine coordination sites: Polymerization and metal-coordination studies (pages 2973–2984)

      Joseph R. Carlise and Marcus Weck

      Article first published online: 10 MAY 2004 | DOI: 10.1002/pola.20134

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      Bipyridine containing norbornenes have been functionalized via metal coordination using a variety of ruthenium(II) and palladium(II) salts. The corresponding monomers have been polymerized in a controlled fashion via ring-opening methathesis polymerization. The solubility of the resulting polyelectrolytes in non-polar solutions could be tuned by alkyl functionalization of the ligands around the metal centers. These polymers present the first poly(norbornene)s containing bipyridine-based metal complexes at each repeating unit and might find numerous applications including luminescent and electroluminescent materials.

    14. New series of highly phenyl-substituted polyfluorene derivatives for polymer light-emitting diodes (pages 2985–2993)

      Qiang Peng, Minggui Xie, Yan Huang, Zhiyun Lu and Dan Xiao

      Article first published online: 10 MAY 2004 | DOI: 10.1002/pola.20111

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      A new series of highly phenyl-substituted polyfluorene derivatives were synthesized through a Suzuki coupling reaction. The resulting polymers exhibited good thermal stability and excellent photoluminescent and electroluminescent properties. The highly phenylated pendants improved the glass-transition temperature of polyfluorene without forming defects in the polymers and reduced their tendency to form aggregate/excimers.

    15. Monomer reactivity ratios for acrylonitrile–methyl acrylate free-radical copolymerization (pages 2994–3001)

      K. B. Wiles, V. A. Bhanu, A. J. Pasquale, T. E. Long and J. E. McGrath

      Article first published online: 10 MAY 2004 | DOI: 10.1002/pola.20149

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      Reactivity ratios for the homogeneous, free-radical initiated copolymerization of acrylonitrile and methyl acrylate were measured by NMR on isolated, low-conversion copolymers and by real-time, in situ Fourier transform infrared (FTIR) spectroscopy. The system used azobisisobutyronitrile initiator in dimethyl formamide at 62 °C. The FTIR technique allowed rapid generation of extensive copolymer compositions, which permitted application of nonlinear least-squares methodology for the first time to this copolymer system. Thus, reactivity ratios at the 95% confidence level were determined to be 1.29 ± 0.2 and 0.96 ± 0.2 for acrylonitrile and methyl acrylate, respectively. The results are useful for the development of acrylonitrile (<90%) melt-processable copolymer fibers and films, which could include precursors for carbon fibers.

    16. High-molecular-weight side-chain liquid-crystalline polyethers based on 4′-cyanobiphenyl-4-oxy mesogenic groups (pages 3002–3012)

      J. M. Montornés, J. A. Reina and J. C. Ronda

      Article first published online: 12 MAY 2004 | DOI: 10.1002/pola.20101

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      A set of poly[ω-(4′-cyano-4-biphenyloxy)alkyl-1-glycidylether]s were synthesized by chemical modification of poly(ω-bromoalkyl-1-glycidylether)s with the sodium salt of 4-cyano-4′-hidroxybiophenyl. New high molecular weight SCLCPs were obtained with excellent yield and almost quantitative degree of modification. The liquid crystalline behavior was analyzed by DSC and POM, and mesophase assignments were confirmed by X-ray diffraction. Polymers that had alkyl spacers with n = 2 and 4 were nematic, those that had spacers with n = 6 and 8 were nematic cybotactic, and those that had longer spacers (n = 10 and 12) were smectic C and showed some crystallization of the side alkyl chains.

    17. New polyurethanes and polyesters for second-order nonlinear optical applications (pages 3013–3022)

      M. Casalboni, U. Caruso, A. De Maria, M. Fusco, B. Panunzi, A. Quatela, A. Roviello, F. Sarcinelli and A. Sirigu

      Article first published online: 12 MAY 2004 | DOI: 10.1002/pola.20137

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      New polyesters and polyurethanes for second-order nonlinear optical applications were synthesized and characterized. All the polymers exhibited high thermal stability and high glass-transition temperatures. For some of the polymers, films of good optical quality were obtained. For these polymers, second harmonic generation measurements were also taken.

    18. Radical copolymerization of cyclic diarsine with vinyl monomers (pages 3023–3028)

      Tomokazu Umeyama, Kensuke Naka and Yoshiki Chujo

      Article first published online: 12 MAY 2004 | DOI: 10.1002/pola.20092

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      The synthesis of a novel organoarsenic polymer is described that contains arsenic atoms in the main chain. Radical copolymerization of a six-membered cyclic diarsine compound, 1,2,4,5-tetramethyltetrahydrodiarsenine (1), with vinyl monomers such as styrene and methyl methacrylate in the presence of 2,2′-azobisisobutyronitrile was carried out. The number-average molecular weights of the copolymer obtained after reprecipitation were estimated to be more than 10,000 by gel permeation chromatography analysis (CHCl3, polystyrene standards). By characterization with 1H NMR and 13C NMR spectra, the copolymer was found to possess no diarsenic linkages in the backbone. The polarity and the conjugative stabilization of the substitution of the vinyl group affected the content of the vinyl monomer unit in the copolymer.

    19. Morphology and temperature responsiveness–swelling relationship of poly(N-isopropylamide–chitosan) copolymers and their application to drug release (pages 3029–3037)

      Chia-Fen Lee, Chia-Jen Wen, Chia-Lung Lin and Wen-Yen Chiu

      Article first published online: 13 MAY 2004 | DOI: 10.1002/pola.20085

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      A chitosan–N-isopropylacrylamide (NIPAAm) copolymer, which was synthesized by using ammonium persulfate as an initiator, showed homogeneous morphology and exhibited the characteristic of a lower critical solution temperature (LCST). The copolymer synthesized by using 2,2′-azobis(2-methylpropionamidine)dihydrochloride as an initiator showed a core–shell morphology and the characteristic of LCST was insignificant. The LCST of the chitosan–NIPAAm copolymer depended on the morphology of the copolymer particles. In addition, the effect of various variables such as the chitosan/NIPAAm weight ratio, the concentration of crosslinking agent, and the pH values on the swelling ratio of chitosan–NIPAAm copolymer disks was investigated. Furthermore, variables such as the chitosan/NIPAAm weight ratio and the concentration of the crosslinking agent significantly influenced the behavior of caffeine loading. Two factors (pore size and swelling ratio) affected the behavior of caffeine release from the chitosan–NIPAAm copolymer disks.

    20. Zeolite-supported metallocene catalyst for ethylene/1-hexene copolymerization (pages 3038–3048)

      Maria De Fátima V. Marques and Ana Beatriz A. S. Marinha

      Article first published online: 12 MAY 2004 | DOI: 10.1002/pola.20160

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      Commercial zeolite acid mordenite was thermally treated for use as a support for (n-BuCp)2ZrCl2 for the further evaluation of ethylene/1-hexene copolymerization. The polymerization time, temperature, and solvent, as well as the addition of tri(isobutyl)aluminum in the hexane medium, were evaluated. The catalytic activity and 1-hexene content in the copolymer synthesized with the supported system were very near those obtained with the homogeneous precursor. A comonomer effect was observed for both systems. The polymerization rate profiles were obtained for ethylene polymerization, and the activation energy and monomer reactivity were calculated.

    21. High-quality poly[2-methoxy-5-(2′-ethylhexyloxy)-p-phenylenevinylene] synthesized by a solid–liquid two-phase reaction: Characterizations and electroluminescence properties (pages 3049–3054)

      Xufeng Wu, Gaoquan Shi, Feng'En Chen, Shaohu Han and Junbiao Peng

      Article first published online: 12 MAY 2004 | DOI: 10.1002/pola.20171

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      Poly[2-methoxy-5-(2′-ethylhexyloxy)-p-phenylenevinylene] (MEH-PPV) with a high molar mass and a low polydispersity was synthesized by a solid–liquid two-phase reaction. The polymer had a long conjugation length. An electroluminescence device, with an indium tin oxide/poly(3,4-ethylenedioxylthiophene) (PEDOT)/MEH-PPV/Ba/Al structure, possessed a medium turn-on voltage of 3.3 V, a high luminance of 550 cd/m2 at 6.1 V, and an external quantum efficiency of 0.57%.

    22. Effect of cocatalyst on the chain microstructure of polyethylene made with CGC-Ti/MAO/B(C6F5)3 (pages 3055–3061)

      Daryoosh Beigzadeh, João B.P. Soares and Thomas A. Duever

      Article first published online: 12 MAY 2004 | DOI: 10.1002/pola.20151

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      Solution polymerization of ethylene in Isopar E using CGC-Ti as catalyst and MAO and B(C6F5)3 as cocatalysts was studied. The effects of the amounts of these cocatalysts on the chain microstructure were investigated. 13C NMR and gel permeation chromatography were used to determine the long-chain branching (LCB) content and the molecular weight distribution (MWD), respectively, of the samples. It was observed that higher concentrations of methylaluminoxane increased the LCB content and decreased the molecular weight of the polymer. However, increasing the amount of B(C6F5)3 lowered the LCB content, increased the molecular weight, and significantly broadened the MWD.

    23. Synthesis and characterization of hyperbranched poly(urea-urethane)s based on AA* and B2B* monomers (pages 3062–3081)

      Mona Abdelrehim, Hartmut Komber, Joseph Langenwalter, Brigitte Voit and Bernd Bruchmann

      Article first published online: 12 MAY 2004 | DOI: 10.1002/pola.20154

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      Hyperbranched aromatic and aliphatic poly(urea-urethane)s have been prepared by the one-pot method using different diisocyanates as AA* and bishydroxyamines as B2B* monomers. Suitable conditions for largerscale synthesis of soluble products could be identified. By NMR analysis the different isomeric structures were deduced for TDI based products, percentages of linear, terminal, and dendritic subunits were calculated, and the degree of branching (DB) was determined with up to 70%.

    24. Synthesis and characterization of epoxidized polybutadiene/polyaniline graft conducting copolymer (pages 3082–3090)

      F. R. De Risi, L. D'Ilario and A. Martinelli

      Article first published online: 12 MAY 2004 | DOI: 10.1002/pola.20150

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      In this article the synthesis and the characterization of an elastomeric conducting material, obtained by grafting polyaniline (EB) on commercial cis-1,4-polybutadiene (PB) were described. Polybutadiene was first partially epoxidized (EPB) in chloroform solution with metachloroperbenzoic acid. The conducting polymer was then grafted to the activated polybutadiene via the aminolysis reaction between the polyaniline NH2 terminal groups and the oxirane rings. The HCl doping of the graft copolymer (EPBPAN) film induced crosslinking reactions, generated by the acid cleavage of unreacted oxirane groups. The electrical conductivity of the doped material reached values of about 10−1 Ω−1 cm−1.