Journal of Polymer Science Part A: Polymer Chemistry

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

15 May 2005

Volume 43, Issue 10

Pages 1985–2193

  1. Articles

    1. Top of page
    2. Articles
    3. Rapid Communications
    1. Characterization of ring-opening polymerization of genipin and pH-dependent cross-linking reactions between chitosan and genipin (pages 1985–2000)

      Fwu-Long Mi, Shin-Shing Shyu and Chih-Kang Peng

      Version of Record online: 30 MAR 2005 | DOI: 10.1002/pola.20669

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      The pH-dependent network segmental variations of genipin-crosslinked chitosan gels: (a) cross-linking at acidic and neutral conditions—the network segments of chitosan gels only consist of short cross-link units; (b) cross-linking at pH 9.0—the network segments of chitosan gels consist of short cross-link units and long cross-link units of polymerized genipin; (c) cross-linking at strongly basic condition—the network segments of chitosan gels only consist of long cross-link unit of polymerized genipin.

    2. Reversible addition–fragmentation chain transfer polymerization of methyl methacrylate in suspension (pages 2001–2012)

      John D. Biasutti, Thomas P. Davis, Frank P. Lucien and Johan P. A. Heuts

      Version of Record online: 30 MAR 2005 | DOI: 10.1002/pola.20673

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      The reversible addition–fragmentation chain transfer (RAFT) polymerization of methyl methacrylate (MMA) mediated by 2-cyanoprop-2-yl dithiobenzoate (CPDB) in bulk (60 and 70 °C) and suspension (70 °C) was studied over a range of CPDB concentrations, and in both polymerization systems, a good control of the molecular weight and polydispersity was observed. The suspension polymerizations were stable, and the particle sizes decreased with increasing CPDB concentration. The livingness of the polymers formed in suspension was proven by successful chain extensions with MMA, styrene, and 2-hydroxyethyl methacrylate.

    3. Kinetic study of the radical polymerization behavior of N-(1-phenylethylaminocarbonyl)methacrylamide (pages 2013–2020)

      Makiko Seno, Takahiro Yamada, Hongwei Wang, Tomohiro Hirano and Tsuneyuki Sato

      Version of Record online: 30 MAR 2005 | DOI: 10.1002/pola.20682

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      N-(1-phenylethylaminocarbonyl)methacrylamide (PEACMA) carrying a conjugative urea moiety is polymerized in DMSO according to conventional radical polymerization kinetics, where PEACMA is considered to associate with DMSO. The homogeneous polymerization system involves ESR-observable propagating radical under the actual polymerization conditions. ESR-determined rate constants of propagation (kp) and termination (kt) are 140 L/mol s and 3.4 × 104 L/mol s at 60 °C. The kp/(kt)1/2 value of PEACMA as a homopolymerizability indicator is rather higher than those of methacrylates and methacrylamides.

    4. Synthesis of poly(arylene thioether)s from protected dithiols and aromatic difluorides with an organic base (pages 2021–2027)

      Insik In and Sang Youl Kim

      Version of Record online: 30 MAR 2005 | DOI: 10.1002/pola.20677

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      High molecular weight poly(arylene thioether)s were prepared from dithiol monomers protected by N-propyl-S-carbamate groups through a nucleophilic aromatic substitution reaction. The protected dithiols were successfully deprotected by an organic base (1,8-diazabicyclo[5.4.0]-7-undecene), and the subsequent polymerization reaction proceeded smoothly, resulting in high molecular weight poly(arylene thioether)s.

    5. Novel thermal curing reaction of oxetane resins with polyfunctional phenols (pages 2028–2037)

      Tadatomi Nishikubo, Hiroto Kudo, Mayu Yoshihara and Ken Maruyama

      Version of Record online: 30 MAR 2005 | DOI: 10.1002/pola.20586

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      The thermal curing reaction of polyfunctional oxetanes (oxetane resins) such as tris[4-(3-ethyloxetane-3-yl)methoxyphenyl]methane (TEOMP) and 1,3,5-tris(3-ethyl-3-oxetanylmethoxy)benzene with certain polyfunctional phenols was performed in bulk with quaternary onium salts as catalysts. The reaction proceeded smoothly at 180–220 °C and produced insoluble gel products, and the rate of gel production increased with the reaction temperature. The thermal properties, such as the glass-transition temperatures and 5 and 10 wt % weight-loss temperatures, of the resulting gel products were confirmed with differential scanning calorimetry and thermogravimetric analysis, and the cured oxetane resins had the expected thermal properties.

    6. Direct synthesis of amphiphilic block copolymers from glycidyl methacrylate and poly(ethylene glycol) by cationic ring-opening polymerization and supramolecular self-assembly thereof (pages 2038–2047)

      Wei Huang, Yongfeng Zhou and Deyue Yan

      Version of Record online: 30 MAR 2005 | DOI: 10.1002/pola.20688

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      Amphiphilic block copolymers composed of hydrophilic poly(ethylene glycol) (PEG) block and hydrophobic poly(glycidyl methacrylate) (PGMA) block were synthesized through cationic ring-opening polymerization. By the control of the reaction time in the synthesis of block copolymer PEG-b-PGMA, a linear GMA block was obtained through the ring-opening polymerization of epoxy groups, whereas the double bond in GMA remained unreacted. The results show that the molecular weights of the PEG precursors have little influence on the grafting of GMA and the PGMA blocks almost keep the same length, despite the difference of PEG blocks. In addition, the PGMA blocks only consisted of several GMA units. The obtained amphiphilic block copolymers of PEG-b-PGMA could form core–shell polymeric micelles by direct molecular self-assembly in water, and the crosslinking of PGMA core of the micelles was also investigated.

    7. Shielded molecularly imprinted polymers prepared with a selective surface modification (pages 2048–2060)

      Yoshiyuki Watabe, Ken Hosoya, Nobuo Tanaka, Takuya Kubo, Takuya Kondo and Masatoshi Morita

      Version of Record online: 30 MAR 2005 | DOI: 10.1002/pola.20674

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      Uniformly sized, molecularly imprinted polymers of bisphenol A were prepared by selective surface modification and immobilized at intervals of functional monomers with 4,4′-methylenebisphenol as a pseudo template. MIPs for BPA were prepared with 4-vinyl pyridine immobilized at the most effective interval and ethylene glycol dimethacrylate monomer as a functional crosslinker, respectively. The MIPs prepared were surface modified with both polar and ionic monomers with different modification methods and then evaluated to reveal their selectivity and retention characteristics.

    8. Influence of the catalyst on monomer insertion in the syndiospecific copolymerization of styrene and para-methylstyrene (pages 2061–2067)

      Jürgen Schellenberg

      Version of Record online: 30 MAR 2005 | DOI: 10.1002/pola.20686

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      The effect of the kind of the transition metal catalyst on the extent of the comonomer insertion in the syndiospecific complex-coordinative copolymerization of styrene and para-methylstyrene has been investigated. The correlation between catalyst structure and comonomer insertion can be described by electronic effects approximated by the electrostatic charge of the transition metal atom (qMe) and steric effects considered by the minimum structural cone angle of the ligand θstr, and r2 reflecting the comonomer insertion. The fitted results indicate that the steric properties of the transition metal complexes have the most important effect on the insertion of para-methylstyrene into the copolymer.

    9. Role of vacuum ultraviolet irradiation in plasma-induced graft polymerization in the pore-filling polymerization of porous materials (pages 2068–2074)

      Teruhiko Kai, Wataru Ueno, Takeo Yamaguchi and Shin-Ichi Nakao

      Version of Record online: 30 MAR 2005 | DOI: 10.1002/pola.20691

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      The role of vacuum ultraviolet (VUV) rays contained in the plasma during plasma-induced graft polymerization in the pores of a porous high-density polyethylene (HDPE) substrate was investigated through the separation of the VUV rays from the plasma with LiF, CaF2, and quartz filters. Two characteristic phenomena, the effect of the solvent on the grafting rate and the graft polymerization inside the porous substrate, were observed in the VUV-induced graft polymerization process. These results provided clear evidence that VUV rays in the plasma played an important role in the formation of grafted layers in the pores of the HDPE substrate.

    10. Alkali metal salt-catalyzed aldol addition of dimethylsilyl enolate on a polyether structure (pages 2075–2084)

      Shin-Ichi Yamamoto, Hidehiko Morita, Sachika Hayashi and Osamu Moriya

      Version of Record online: 30 MAR 2005 | DOI: 10.1002/pola.20692

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      The aldol addition of dimethylsilyl enolates to aldehydes with alkali metal salt catalysts was examined. Several kinds of polyether derivatives were employed as solid solvents without a liquid one. The results demonstrated that the presence of polyether structures provided a favorable reaction environment and enabled the reaction under solvent-free conditions.

    11. Novel family of triphenylamine-containing, hole-transporting, amorphous, aromatic polyamides with stable electrochromic properties (pages 2085–2098)

      Tzy-Hsiang Su, Sheng-Huei Hsiao and Guey-Sheng Liou

      Version of Record online: 5 APR 2005 | DOI: 10.1002/pola.20666

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      Novel electrochromic aromatic poly(amine amide)s with pendent triphenylamine units were prepared via direct phosphorylation polycondensation from N,N-bis(4-aminophenyl)-N′,N′-diphenyl-1,4-phenylenediamine and various aromatic dicarboxylic acids. All the poly(amine amide)s were amorphous and could be solution-cast into transparent and flexible films with good mechanical properties. They exhibited good thermal stability and relatively high glass-transition temperatures (263–290 °C). The polymer thin films showed electrochromic behavior when a linear potential sweep was applied; their color changed from pale yellow to green and then blue at electrode potentials of 0.65 and 1.03 V, respectively.

    12. Poly(epichlorohydrin) modified with 3,4,5-tris(dodecyloxy)benzoate: The structure and dynamics of the aliphatic side chains in the columnar mesophase (pages 2099–2111)

      Marta Giamberini, Joan Carles Ronda and José Antonio Reina

      Version of Record online: 7 APR 2005 | DOI: 10.1002/pola.20680

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      The dynamics and structure of the aliphatic side chains of a copolymer, obtained through the chemical modification of poly(epichlorohydrin) with 3,4,5-tris(dodecyloxy)benzoate, were investigated with solid-state 13C NMR. Below 323 K, the polymer exhibited a columnar mesophase, and below 283 K, the aliphatic chains partially crystallized in an all-anti conformation. The melting of the side chain did not affect the mesophase order, but only the inner carbon atoms in the side chain seemed to acquire high conformational mobility in the molten state.

    13. Dependence of the pretreatment efficiency of polymer-based adsorbents for environmental water on their uniformity and size (pages 2112–2118)

      Takuya Kubo, Ken Hosoya, Yoshiyuki Watabe, Nobuo Tanaka, Tomoharu Sano and Kunimitsu Kaya

      Version of Record online: 7 APR 2005 | DOI: 10.1002/pola.20685

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      Polymer-based adsorbents having excellent size uniformity were utilized as pretreatment media for real environmental water containing numerous contaminants. According to the comparison of results with those in “an ideal approach” with high performance liquid chromatography (HPLC), it was suggested that the size uniformity as well as the largeness of adsorbents were significantly important in point of the loading pressure on treating the environmental water. Furthermore, it was found that one of the uniformly sized polymer adsorbents realized even comparable efficiency to those with a commercially available adsorbent based on a typical silica-based ODS stationary phase.

    14. Synthesis and photophysical properties of polyfluorenes bearing silicon-based functional groups (pages 2119–2127)

      Koji Takagi, Satoshi Kunii and Yasuo Yuki

      Version of Record online: 7 APR 2005 | DOI: 10.1002/pola.20689

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      Five polyfluorenes bearing bulky trimethylsilyl (PTMS1 and PTMS2), tris(trimethylsilyl)silyl (PTTMS1), and silsesquioxane groups (PPOSS1 and PPOSS2) were synthesized. The photophysical properties were investigated in the solution and solid states. While polyfluorenes bearing trimethylsilyl group were susceptible to the green-light emission, PPOSS2 emitted a pure blue-light in the film state and even after the thermal treatment.

    15. Ethylene polymerization over supported catalysts [2,6-bis(imino)pyridyl iron dichloride/magnesium dichloride] with AlR3 as an activator (pages 2128–2133)

      Tatiana B. Mikenas, Vladimir A. Zakharov, Lyudmila G. Echevskaya and Michail A. Matsko

      Version of Record online: 8 APR 2005 | DOI: 10.1002/pola.20687

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      Supported LFeCl2/MgCl2 catalysts {L = 2,6-bis[1-(2,6-dimethylphenylimino)ethyl]pyridyl} have been formed through the interaction of the LFeCl2 complex with the surface acidic sites of MgCl2. These catalysts with AlR3 (R = Me, Et, i-Bu, or n-Oct) as an activator exhibit high activity in ethylene polymerization at 80 °C (up to 300 kg/g of Fe h bar of C2H4) and produce polyethylene with a good morphology, a broad molecular mass distribution (weight-average molecular weight/number-average molecular weight = 9.3–23.3), and a high concentration of terminal vinyl groups (0.4–0.5 C[DOUBLE BOND]C/1000 C). The activity remarkably increases with the addition of H2 (ca. 1.5–2 times).

    16. Living radical photopolymerization induced grafting on thiol–ene based substrates (pages 2134–2144)

      Sirish K. Reddy, Robert P. Sebra, Kristi S. Anseth and Christopher N. Bowman

      Version of Record online: 7 APR 2005 | DOI: 10.1002/pola.20693

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      Reactive substrates, which can be used for surface modification, have been formed through the curing of thiol–ene and acrylate systems in the presence of the photoiniferter p-xylene bis(N,N-diethyl dithiocarbamate) (XDT). In the presence of XDT, the thiol–ene systems photopolymerize more quickly than the traditional acrylate and methacrylate systems by one to two orders of magnitude. The photopatterning of dithiocarbamate-incorporated thiol–ene substrates has yielded a wide range of surface properties, ranging from hydrophilic to hydrophobic surfaces.

    17. Synthesis of polymeric microspheres from a Merrifield resin by surface-initiated nitroxide-mediated radical polymerization (pages 2145–2154)

      Kejian Bian and Michael F. Cunningham

      Version of Record online: 7 APR 2005 | DOI: 10.1002/pola.20694

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      Polystyrene and its copolymers with methyl methacrylate and 2-hydroxyethyl methacrylate were grafted onto a Merrifield resin via nitroxide-mediated radical polymerization. The microspheres increased in size with the molecular weight of the bulk polymer, although the grafting was not confined to the surface.

    18. Synthesis and characterization of alt-copoly(carbosiloxane)s containing oligodiphenylsiloxane segments (pages 2155–2163)

      Thomas M. Gädda and William P. Weber

      Version of Record online: 8 APR 2005 | DOI: 10.1002/pola.20665

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      Novel α,ω-divinyloligodiphenylsiloxanes were prepared, characterized, and copolymerized by Pt-catalyzed hydrosilylation with α,ω-dihydridopentasiloxanes. The oligomer and polymer structures were determined with 1H, 13C, 19F, and 29Si NMR and IR spectrometry. The polymers had high thermal stability in both air and nitrogen.

    19. Structure of poly(L-lactic acid)s prepared by the dehydropolycondensation of L-lactic acid with organotin catalysts (pages 2164–2177)

      S. Shyamroy, B. Garnaik and S. Sivaram

      Version of Record online: 8 APR 2005 | DOI: 10.1002/pola.20679

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      The synthesis of low-molecular-weight (weight-average molecular weight < 45,000 g/mol) lactic acid polymers by dehydropolycondensation of L-lactic acid was investigated. The products were characterized by DSC, SEC, VPO, 13C NMR and MALDI-TOF. Tetraphenyl tin was an effective transesterification catalyst and randomization of the stereosequence at 190 °C was observed. In contrast distannoxane catalyst caused comparatively less transesterification reaction and randomization of the stereosequences was slow even at 190 °C. The MALDI-TOF spectra of poly(L-lactic acid) (PLA) chains doped with Na+ and K+ cations showed that the PLA chains had the expected end groups. Furthermore, the MALDI-TOF spectra enabled the simultaneous detection of the cyclic oligomers of PLA present in these samples, thus achieving the full structural characterization of the molecular species in poly(L-lactic acid)s.

    20. Ultrafast single-electron-transfer/degenerative-chain-transfer mediated living radical polymerization of acrylates initiated with iodoform in water at room temperature and catalyzed by sodium dithionite (pages 2178–2184)

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

      Version of Record online: 8 APR 2005 | DOI: 10.1002/pola.20655

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      The first example of the single-electron-transfer/degenerative-chain-transfer mediated living radical polymerization of acrylates catalyzed by Na2S2O4/NaHCO3 is reported. This polymerization is initiated with iodoform (CHI3) and carried out in water (H2O) at 23–30 °C. A quantitative monomer conversion can be achieved in 2–3 h. This synthetic method produces telechelic α,ω-di(iodo)polyacrylates, with a number-average molecular weight as high as 800,000 and with a weight-average molecular weight/number-average molecular weight ratio of 1.15, that can serve as macroinitiators.

  2. Rapid Communications

    1. Top of page
    2. Articles
    3. Rapid Communications
    1. Synthesis of ultrahigh molar mass, structural defects free poly(vinyl chloride) with high syndiotacticity and glass transition temperature by single electron transfer–degenerative chain transfer living radical polymerization (SET–DTLRP) (pages 2185–2187)

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

      Version of Record online: 8 APR 2005 | DOI: 10.1002/pola.20650

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      SET–DTLRP of VC initiated with CHI3 and catalyzed by Na2S2O4 in water at 21 °C produces ultrahigh molar mass poly(vinyl chloride) (PVC). These PVCs with Mn of 160,000–200,000 have higher glass transition temperature and thermal stability than the highest molecular weight PVC that is commercially available (Mn = 113,000).

    2. Miniemulsion reversible addition fragmentation chain transfer polymerization of vinyl acetate (pages 2188–2193)

      James P. Russum, Nicholas D. Barbre, Christopher W. Jones and F. Joseph Schork

      Version of Record online: 8 APR 2005 | DOI: 10.1002/pola.20681

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      Poly(vinyl acetate) was produced in a controlled manner using RAFT chemistry in a miniemulsion system. Homogeneous nucleation of the vinyl acetate monomer was suppressed through the use of an oil soluble initiator, 2,2′azo-bis(isobutyronitrile). The miniemulsion polymerizations exhibited lower reaction rates than a bulk polymerization.

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