Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Journal of Polymer Science Part A: Polymer Chemistry

15 April 2005

Volume 43, Issue 8

Pages 1545–1744

  1. Articles

    1. Top of page
    2. Articles
    3. Rapid Communication
    1. Synthesis and characterization of proton-conducting copolyimides bearing pendant sulfonic acid groups (pages 1545–1553)

      Yan Yin, Otoo Yamada, Yoshiki Suto, Takashi Mishima, Kazuhiro Tanaka, Hidetoshi Kita and Ken-ichi Okamoto

      Version of Record online: 23 FEB 2005 | DOI: 10.1002/pola.20634

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      A series of sulfonated (co)polyimides (SPIs) bearing pendant sulfonic acid groups were synthesized from 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA), bis(3-sulfopropoxy) benzidine monomers (BSPB), and common nonsulfonated diamines via statistical or sequenced polycondensation reactions. Their solubility behaviors, proton conductivity, water uptake, and dimensional change in water were investigated. Membranes with reasonably high proton conductivity and improved dimensional stability were successfully developed.

    2. Observation of optical activity in polythiourethane obtained by the controlled cationic ring-opening polymerization of chiral cyclic thiourethane derived from serine (pages 1554–1561)

      Atsushi Nagai, Bungo Ochiai and Takeshi Endo

      Version of Record online: 23 FEB 2005 | DOI: 10.1002/pola.20624

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      A chiral polythiourethane synthesized by the controlled cationic ring-opening polymerization of cyclic thiourethane was evaluated with 1H NMR, IR, and circular dichroism spectroscopy. The regulated nature of the chiral polythiourethane depended on the hydrogen bonds between the carbonyl and NH groups in the thiourethane group.

    3. Syndiospecific polymerization of styrene with Cp*TiCl((OCH(R)CH2)2NAr)/MMAO (pages 1562–1568)

      Jie Chen, Zhan-Jiang Zheng, Li Pan, Ding Pan and Yue-Sheng Li

      Version of Record online: 23 FEB 2005 | DOI: 10.1002/pola.20621

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      A series of new titanium complexes Cp*TiCl((OCH(R)CH2)2NAr) has been synthesized and characterized, and is shown to be a highly active catalyst for the syndiospecific polymerization of styrene.

    4. Self-assembly of oligo(p-phenylenevinylene)-block-poly(ethylene oxide) in polar media and solubilization of an oligo(p-phenylenevinylene) homooligomer inside the assembly (pages 1569–1578)

      Takeshi Mori, Takushi Watanabe, Keiji Minagawa and Masami Tanaka

      Version of Record online: 1 MAR 2005 | DOI: 10.1002/pola.20631

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      Diblock copolymers consisting of oligo(p-phenylenevinylene) (OPV) and poly(ethylene oxide) (PEO) were synthesized, and their assembling properties in polar media were studied. Depending on the PEO chain length, the assembled structure of the copolymers changed from a cylinder to a sphere. The block copolymer could solubilize an OPV homooligomer in the core of the cylindrical assembly.

    5. Donor–acceptor-based poly(toluidine-co-chloroaniline)s: Synthesis and characterization (pages 1579–1587)

      P. Savitha and D. N. Sathyanarayana

      Version of Record online: 1 MAR 2005 | DOI: 10.1002/pola.20627

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      A series of poly(o-/m-toluidine-co-o-/m-chloroaniline) copolymers of different compositions were synthesized by an emulsion method with ammonium persulfate as the oxidant. The conductivity of the copolymers was two to five orders of magnitude higher than that of the homopolymers poly(o-toluidine) and poly(m-chloroaniline). A copolymer of o-toluidine and m-chloroaniline synthesized with a 1:1 comonomer feed ratio exhibited the highest conductivity (0.14 S cm−1).The properties of the copolymers were influenced by the positions of the substituents and the concentrations of the individual monomers in the feed.

    6. Ambient-temperature copper-catalyzed atom transfer radical polymerization of methacrylates in ethylene glycol solvents (pages 1588–1598)

      Solomon M. Kimani and Stephen C. Moratti

      Version of Record online: 1 MAR 2005 | DOI: 10.1002/pola.20625

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      The use of ethylene glycol solvents in the room-temperature atom transfer radical polymerization (ATRP) of various hydrophobic and hydrophilic methacrylates is demonstrated. Unlike many of the very polar solvents described in the literature for room-temperature ATRP, these solvents have good solvency for a wide range of polymers and monomers and are cheap and relatively nontoxic. A wide range of polar and non-polar methacrylates were polymerized to high MW and conversion and low polydispersity using this system. The electrochemical behavior of copper complexes in selected solvents is examined to determine why ethylene glycol solvents provide good polymerization rates at room temperature.

    7. Effect of alkylaluminum on ethylene polymerization catalyzed by 2,6-bis(imino)pyridyl complexes of Fe(II) (pages 1599–1606)

      Qi Wang, Lidong Li and Zhiqiang Fan

      Version of Record online: 1 MAR 2005 | DOI: 10.1002/pola.20626

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      The bimodal molecular weight distribution of polyethylene prepared by iron complexes [(ArN[DOUBLE BOND]C(Me))2C5H3N]FeCl2 [Ar[DOUBLE BOND]2,6-diisoporpylphenyl (1) and 2,6-dimethylphenyl (2)] activated by tetraethylaluminoxane (TEAO) was generated through mechanism of chain transfer to residual triethylaluminum in TEAO. The ratios of rate constants of chain transfer to aluminum to chain propagation (ktrA/kp) were determined to be 0.12 and 2.48 for iron complexes 1 and 2, which are far larger than that for metallocene-based catalysts. It has been concluded from great difference between 1 and 2 upon the ktrA/kp ratio that iron complex with less congested aryl substituents is subjected to chain transfer to aluminum.

    8. Unusual inorganic phase formation in ultraviolet-curable organic–inorganic hybrid films (pages 1607–1623)

      Zhengang Zong, Mark D. Soucek and Chenchen Xue

      Version of Record online: 1 MAR 2005 | DOI: 10.1002/pola.20664

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      Inorganic–organic hybrid materials were prepared using a cycloaliphatic epoxide adduct of linseed oil with tetraethylorthosilicate (TEOS) oligomers via a cationic UV-curing process. The microscopy and dynamic mechanical data indicated that the inorganic phase size distribution of the hybrid films was bimodal. It was surmised that the bimodal distribution was a consequence of the rapidity vitrification of the organic phase.

    9. Novel network morphology of poly(p-oxybenzoyl) (pages 1624–1634)

      Kunio Kimura, Shin-ichiro Kohama, Satomi Kondoh, Tetsuya Uchida, Yuhiko Yamashita, Takeshi Oohazama and Yoshimitsu Sakaguchi

      Version of Record online: 4 MAR 2005 | DOI: 10.1002/pola.20639

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      A novel network structure of poly(p-oxybenzoyl) was successfully prepared by the polymerization of 4-acetoxybenzoic acid with 3,5-diacetoxybenzoic acid at a concentration in the feed (χf) of 0.10–0.15. Polymerizations were carried out at a concentration of 1.0% in an aromatic solvent at 320 °C. The network structure was comprised of spheres connected by fibrillar crystals and possessed high crystallinity. Co-oligomers were first precipitated in the beginning of the polymerization by liquid–liquid phase separation to form microdroplets. The fibrillar crystals were formed in the coalesced spheres by the crystallization of oligomers. The fibrillar crystals connecting the spheres gradually appeared owing to the shrinkage of the spheres. The fibrillar crystals grew from the surface of the spheres with the crystallization of homo-oligomers of 4-oxybenzoyl units, and finally the network structure was completed.

    10. Oxidative coupling polymerization of 2,3-dihydroxynaphthalene with dinuclear-type copper(II) catalyst (pages 1635–1640)

      Shigeki Habaue, Ryo Muraoka, Akiko Aikawa, Soichiro Murakami and Hideyuki Higashimura

      Version of Record online: 4 MAR 2005 | DOI: 10.1002/pola.20637

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      The oxidative coupling polymerization of 2,3-dihydroxynaphthalene with novel dinuclear-type copper(II) catalysts successfully produced poly(2,3-dihydroxy-1,4-naphthylene) in good yields. The structure of the tetraamine ligands, the monomer, and the counter anion of the copper(II) salt significantly influenced the catalyst activity.

    11. Temperature-sensitive hydrogel microspheres formed by liquid–liquid phase transitions of aqueous solutions of poly(N,N-dimethylacrylamide-co-allyl methacrylate) (pages 1641–1648)

      Xiangchun Yin and Harald D. H. Stöver

      Version of Record online: 4 MAR 2005 | DOI: 10.1002/pola.20523

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      Aqueous solutions of poly(N,N-dimethylacrylamide-co-allyl methacrylate) copolymers showed liquid–liquid phase transitions upon heating. Hydrogel microspheres were prepared by the free-radical crosslinking of phase-separated liquid microdroplets.The formed microspheres were found to be thermoresponsive and may find applications in protein separation and controlled delivery.

    12. Accelerated synthesis of poly(methyl methacrylate)-b-poly(vinyl chloride)-b-poly(methyl methacrylate) block copolymers by the CuCl/tris(2-dimethylaminoethyl)amine-catalyzed living radical block copolymerization of methyl methacrylate initiated with α,ω-di(iodo)poly(vinyl chloride) in dimethyl sulfoxide at 90 °C (pages 1649–1659)

      Virgil Percec, Tamaz Guliashvili, Anatoliy V. Popov, Ernesto Ramirez-Castillo, Jorge F. J. Coelho and Luis A. Hinojosa-Falcon

      Version of Record online: 4 MAR 2005 | DOI: 10.1002/pola.20616

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      Poly(methyl methacrylate)-b-poly(vinyl chloride)-b-poly(methyl methacrylate) (PMMA-b-PVC-b-PMMA) block copolymers [number-average molecular weight (Mn) = 41,000–106,700] were synthesized in 30–70 min via the CuCl/tris(2-dimethylaminoethyl)amine (Me6-TREN)-catalyzed living radical block copolymerization of methyl methacrylate (MMA) initiated with α,ω-di(iodo)poly(vinyl chloride) (Mn = 2100–20,000) in dimethyl sulfoxide (DMSO) at 90 °C.

    13. Ultrafast synthesis of poly(methyl methacrylate)-b-poly(vinyl chloride)-b-poly(methyl methacrylate) block copolymers by the Cu(0)/tris(2-dimethylaminoethyl)amine-catalyzed living radical block copolymerization of methyl methacrylate initiated with α,ω-di(iodo)poly(vinyl chloride) in the presence of dimethyl sulfoxide at 25 °C (pages 1660–1669)

      Virgil Percec, Tamaz Guliashvili, Anatoliy V. Popov, Ernesto Ramirez-Castillo and Luis A. Hinojosa-Falcon

      Version of Record online: 4 MAR 2005 | DOI: 10.1002/pola.20615

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      Poly(methyl methacrylate)-b-poly(vinyl chloride)-b-poly(methyl methacrylate) (PMMA-b-PVC-b-PMMA) block copolymers (number-average molecular weight = 49,100–134,800) were synthesized in 60–100 min via the Cu(0)/tris(2-dimethylaminoethyl)amine (Me6-TREN)-catalyzed living radical block copolymerization of methyl methacrylate (MMA) initiated with α,ω-di(iodo)poly(vinyl chloride) (number-average molecular weight = 2100–29,800) in dimethyl sulfoxide (DMSO) at 25 °C. At 90 °C, the complete conversion of MMA took 15 min.

    14. Polyurethane–nanosilica hybrid nanocomposites synthesized by frontal polymerization (pages 1670–1680)

      Su Chen, Jianjun Sui, Li Chen and John A. Pojman

      Version of Record online: 4 MAR 2005 | DOI: 10.1002/pola.20628

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      Polyurethane–nanosilica hybrids were synthesized with frontal polymerization. Structurally well-dispersed and stable hybrids were obtained via a two-step functionalization process: First, the silica was encapsulated with 3-aminopropyltriethoxysilane (APTS). Second, poly(propylene oxide) glycol, toluene 2,4-diisocyanate, 1,4-butanediol, and a catalyst (stannous caprylate) were dissolved in dimethylbenzene and mixed together at room temperature along with the modified nanosilica. A constant-velocity propagating front was initiated via the heating of the end of the tubular reactor. For the complete encapsulation of the silica with APTS, different weight ratios of APTS to silica were investigated. The polyurethane hybrids were characterized with Fourier transform infrared, differential scanning calorimetry, and transmission electron microscopy. The polyurethane hybrids produced by frontal polymerization had the same properties as those produced by batch polymerization with stirring, but the frontal polymerization method required significantly less time and lower energy input than the batch polymerization method.

    15. Copolymerization of ethylene and cyclopentene with bis(β-enaminoketonato) titanium complexes (pages 1681–1689)

      Li-Ming Tang, Yi-Qun Duan, Li Pan and Yue-Sheng Li

      Version of Record online: 4 MAR 2005 | DOI: 10.1002/pola.20630

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      The copolymerizations of ethylene and cyclopentene with the bis(β-enaminoketonato) titanium complexes [(Ph)NC(R2)CHC(R1)O]2TiCl2 have been investigated. The high molecular weight copolymers with cis-1,2 cyclopentene units were obtained.

    16. Synthesis of polyethylene-octene elastomer/SiO2-TiO2 nanocomposites via in situ polymerization: Properties and characterization of the hybrid (pages 1690–1701)

      Chin-San Wu

      Version of Record online: 4 MAR 2005 | DOI: 10.1002/pola.20649

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      A silicic acid and tetra isopropyl ortho titanate ceramic precursor and a polyethylene-octene elastomer (POE) or acrylic acid grafted polyethylene-octene elastomer (POE-g-AA) were used for preparing hybrids (POE/SiO2[BOND]TiO2 and POE-g-AA/SiO2[BOND]TiO2) via an in situ sol-gel process, with a view to improving thermal and mechanical properties. Hybrids with 10 wt % SiO2[BOND]TiO2 gave the maximum values of tensile strength and glass transition temperature. At higher wt %, excess SiO2[BOND]TiO2 particles caused separation between the organic and inorganic phases.

    17. Synthesis and characterization of novel nano size electroactive poly 4,4′-diaminodiphenyl sulphone (pages 1702–1707)

      P. Manisankar, C. Vedhi and G. Selvanathan

      Version of Record online: 8 MAR 2005 | DOI: 10.1002/pola.20643

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      The modification of electrodeposited polyaniline film by subsequent electrodeposition of 4,4′-diaminodiphenyl sulfone (DDS) leads to a new material having nanostructure. The coated polymer films were treated with various pH solutions. The film adherent characteristics and surface morphology were studied using SEM. The electrochemically synthesized polyDDS revealed good redox behavior. The DDS was also polymerized by the chemical oxidation method using potassium persulphate. The polymer was characterized by UV-Vis and FTIR spectral studies. The formation of polymer through the N[BOND]H group was understood from the single N[BOND]H stretching vibrational frequency at 3459 cm−1. The X-ray diffraction studies revealed the formation of nano sized (28 nm) crystalline polymer. The conductivity of the polymer was determined to be 1.07 × 10−4 S.cm−1. The solubility of the chemically polymerized powder was ascertained, and polyDDS showed good solubility in DMF and DMSO.

    18. Synthesis of three-armed poly(trans-4-hydroxy-N-benzyloxycarbonyl-L-proline)-block-poly(ε-caprolactone) copolymers (pages 1708–1717)

      Ren-Shen Lee and Jen-Ming Yang

      Version of Record online: 8 MAR 2005 | DOI: 10.1002/pola.20642

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      A series of novel types of three-armed PHpr-b-PCL were successfully synthesized via melt block copolymerization of trans-4-hydroxy-N-benzyloxycarbonyl-L-proline (N-CBz-Hpr) and ε-caprolactone (ε-CL) with a trifunctional initiator trimethylolpropane (TMP) and stannous octoate (SnOct2) as a catalyst.

    19. Synthesis of Davankov-type hypercrosslinked resins using different isomer compositions of vinylbenzyl chloride monomer, and application in the solid-phase extraction of polar compounds (pages 1718–1728)

      Núria Fontanals, Jaime Cortés, Marina Galià, Rosa Maria Marcé, Peter A. G. Cormack, Francesc Borrull and David C. Sherrington

      Version of Record online: 8 MAR 2005 | DOI: 10.1002/pola.20646

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      Two hypercrosslinked resins (HXLGp and HXLGmix) were prepared from two gel-type precursors, which were synthesized using different monomers: p-vinylbenzyl chloride or a mixture of VBC isomers (∼70% m-; ∼30% p-), respectively. The resultant resins showed differences in specific surface area and degree of hydrophilicity. The sorption properties of the two hypercrosslinked resins were compared between them and to another macroporous and hypercrosslinked sorbent. The best results were for the resin (HXLGp) that combines a relatively high specific surface area (908 m2 g−1) and somewhat higher oxygen content (3.96 wt.% O).

    20. Unusual cationic copolymerization behavior of a six-membered ring spiro-orthocarbonate bearing adamantane backbones with a monofunctional epoxide (pages 1729–1740)

      Tetsuo Hino, Yoshinori Ito and Takeshi Endo

      Version of Record online: 8 MAR 2005 | DOI: 10.1002/pola.20633

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      Copolymerization of a six-membered ring spiro-orthocarbonate bearing adamantane backbones and a monofunctional epoxide in the presence of cationic initiators under various reaction conditions was carried out. As a result, the polymerization was found to proceed with unusual cationic copolymerization behavior, in which no expected reaction giving the corresponding polycarbonate was formed.

  2. Rapid Communication

    1. Top of page
    2. Articles
    3. Rapid Communication
    1. Synthesis and properties of novel sulfonated poly(phenylene ether) (pages 1741–1744)

      Kenji Miyatake, Hua Zhou and Masahiro Watanabe

      Version of Record online: 8 MAR 2005 | DOI: 10.1002/pola.20623

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      A novel sulfonated poly(phenylene ether) has been synthesized, and its properties have been investigated. The sulfonated polymer has an ion-exchange capacity of 0.73 mequiv/g and produces a transparent, tough, and flexible membrane. The polymer membrane shows good thermal, hydrolytic, and oxidative stability. High proton conductivity (up to 6.5 × 10−2 S cm−1 at 100 °C) can be obtained at 100% relative humidity. These properties of the polymer membrane prove its potential availability for applications in high-temperature-operating polymer electrolyte fuel cells.

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