Journal of Polymer Science Part A: Polymer Chemistry

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

1 October 2003

Volume 41, Issue 19

Pages 2905–3121

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      Topological polymer chemistry by electrostatic self-assembly (pages 2905–2917)

      Yasuyuki Tezuka

      Version of Record online: 6 AUG 2003 | DOI: 10.1002/pola.10893

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      Recent developments in topological polymer chemistry are outlined. First, nonlinear polymer topologies of randomly coiled, flexible polymer molecules with cyclic and branched structures are systematically classified and various pairs of topological isomers are identified. An electrostatic self-assembly and covalent fixation strategy has subsequently been developed for the efficient synthesis of a variety of topologically unique polymers by making use of new telechelics with moderately strained cyclic onium salt groups carrying multifunctional carboxylate counteranions. Further extensions of topological polymer chemistry have been achieved by the use of cyclic telechelics (kyklo-telechelics) and cyclic macromonomers.

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    1. Self-organized liquid-crystalline polyethers obtained by grafting tapered mesogenic groups onto poly(epichlorohydrin): Toward biomimetic ion channels (pages 2918–2929)

      Joan Carles Ronda, José Antonio Reina, Virginia Cádiz, Marta Giamberini and Luigi Nicolais

      Version of Record online: 7 AUG 2003 | DOI: 10.1002/pola.10888

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      A set of high-molecular weight new-side chain liquid-crystalline polyethers was obtained by chemical modification of poly(epichlorohydrin) (PECH) with potassium 3,4,5-tris(dodecyloxy)benzoate. All copolymers had a nematic columnar mesophase whose range of stability depended on the modification degree. X-ray diffraction experiments and density measurements showed that tapered groups were tilted with respect to the column axes and that the number of disks per unit cell decreased as the modification degree increased.

    2. Synthesis and properties of biodegradable copolymers based on 4,4′-(adipoyldioxy)dicinnamic acid, 1,6-hexanediol, and poly(ethylene glycol)s (pages 2930–2938)

      Minoru Nagata and Sigeki Hizakae

      Version of Record online: 7 AUG 2003 | DOI: 10.1002/pola.10884

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      A series of biodegradable CAC6 block copolymers were prepared by high-temperature solution polycondensation of a diacyl chloride of 4,4′-(adipoyldioxy)-dicinnamic acid (CAC) and 1,6-hexanediol with poly(ethylene glycol)s of various molecular weights (1000–8300). All copolymers could undergo photocuring by ultraviolet light irradiation (λ > 280 nm). The CAC6/E2000(50/50) copolymer film photocured for 3 min exhibited a good elastic property with a maximum tensile strength of 3.7 MPa and maximum elongation of 640%. It is promising as a novel biodegradable elastomer for environmental applications.

    3. Amphiphilic block and statistical siloxane copolymers with antimicrobial activity (pages 2939–2948)

      Georges Sauvet, Witold Fortuniak, Krzysztof Kazmierski and Julian Chojnowski

      Version of Record online: 7 AUG 2003 | DOI: 10.1002/pola.10895

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      Statistical and block all-siloxane copolymers containing quaternary ammonium (QAS) groups with biocidal activity as lateral substituents were synthesized for the study of the effect of the arrangement of the QAS groups in the copolymer chain on their antimicrobial activity. The bioactive siloxane unit was [3-n-octyldimethylammoniopropyl]-methylsiloxane, obtained by the quaternization of tertiary amines by 3-chloropropyl or 3-bromopropylmethylsiloxane units in the polymer chain. All model siloxane copolymers showed high bactericidal activity in a water solution toward the gram-negative bacteria Escherichia coli and the gram-positive bacteria Staphylococcus aureus. However, no essential differences in the activities of the copolymers with block and statistical arrangements of units were detected.

    4. Living free-radical polymerization (reversible addition–fragmentation chain transfer) of 6-[4-(4′-methoxyphenyl)phenoxy]hexyl methacrylate: A route to architectural control of side-chain liquid-crystalline polymers (pages 2949–2963)

      Xiaojuan Hao, Johan P. A. Heuts, Christopher Barner-Kowollik, Thomas P. Davis and Evan Evans

      Version of Record online: 8 AUG 2003 | DOI: 10.1002/pola.10894

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      Side-chain liquid-crystalline polymers of 6-[4-(4′-methoxyphenyl)phenoxy]hexyl methacrylate with controlled molecular weights and narrow polydispersities were prepared via reversible addition–fragmentation chain transfer (RAFT) polymerization with 2-(2-cyanopropyl) dithiobenzoate as the RAFT agent. Differential scanning calorimetry studies showed that the polymers produced via the RAFT process had a narrower thermal stability range of the liquid-crystalline mesophase than the polymers formed via conventional free-radical polymerization. In addition, a chain length dependence of this stability range was found. The generated RAFT polymers displayed optical textures similar to those of polymers produced via conventional free-radical polymerization.

    5. Terpyridine-modified poly(vinyl chloride): Possibilities for supramolecular grafting and crosslinking (pages 2964–2973)

      Michael A. R. Meier and Ulrich S. Schubert

      Version of Record online: 8 AUG 2003 | DOI: 10.1002/pola.10881

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      A schematic representation of functionalized poly(vinyl chloride) (PVC) as it was used for this study. The functionalized material contained metal-ion binding sites, which could be used for crosslinking reactions with transition-metal ions. The complexation of the modified PVC with several transition-metal ions was studied with ultraviolet–visible spectroscopy and gel permeation chromatography.

    6. Characterization of an unsaturated low-density polyethylene (pages 2974–2984)

      A. Smedberg, T. Hjertberg and B. Gustafsson

      Version of Record online: 18 AUG 2003 | DOI: 10.1002/pola.10865

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      This study has concerned the characterization of a new group of low density polyethylenes (LDPE). The new LDPE is a copolymer between ethylene and 1,9-decadiene. The resulting LDPE contains a higher content of vinyl groups. The structure of this copolymer is here illustrated schematically; i.e. vinyl groups are situated on pendant side chains, homogeneously distributed along the backbone chain.

    7. Contribution of steric and electrostatic repulsion forces to the stability of styrene latices copolymerized with acrylic acid (pages 2985–2995)

      X. E. E. Reynhout, L. Hoekstra, J. Meuldijk and A. A. H. Drinkenburg

      Version of Record online: 12 AUG 2003 | DOI: 10.1002/pola.10889

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      Acrylic acid is used in many emulsion polymerization formulations to improve the colloidal stability of the latex product. The strength of electrostatic and steric repulsion forces in a styrene/acrylic acid copolymer latex was investigated at different pH values, electrolyte concentrations, and temperatures. Introduction of acrylic acid during the polymerization proves to provide significant steric and additional electrostatic stability. Relatively high electrolyte levels can destabilize the PS/AA latexes by causing significant flocculation, and at temperatures above the critical coagulation temperature (CCT) of 35 °C flocculation becomes aggregation, which is followed by coalescence.

    8. Synthesis and spectral and thermal properties of copolymers of (2-cyclopentylidene-1,3-dioxolane-4-yl)methyl methacrylate with styrene and acrylonitrile and the determination of the monomer reactivity ratios (pages 2996–3005)

      Zülfiye İlter, Cengiz Soykan and Murat Koca

      Version of Record online: 12 AUG 2003 | DOI: 10.1002/pola.10892

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      The monomer (2-cyclopentylidene-1,3-dioxolane-4-yl)methyl methacrylate (CPDMMA) was synthesized by the reaction of (2-cyclopentylidene-5-hydroxymethyl-1,3-dioxolane) with methacryloyl chloride in the presence of pyridine at 0 °C. The radical-initiated copolymerization of CPDMMA with styrene and acrylonitrile was carried out in a 1,4-dioxane solution at 60 °C with 2,2′-azobisisobutyronitrile as an initiator with different monomer-to-monomer ratios in the feed. The copolymer composition was evaluated by the nitrogen content, and the peak integrations of 1H NMR signals in the polymers led to the determination of the reactivity ratios. The reactivity ratios of the monomers were determined by the application of the Fineman–Ross and Kelen–Tüdös linear methods and the Tidwell–Mortimer nonlinear method. The thermogravimetric analysis of the copolymers revealed that the thermal stability of the two copolymer systems decreased with an increase in the molar fraction of CPDMMA in the copolymers.

    9. Immiscible polymers in double spin-coated electroluminescent devices containing phenyl-substituted tris(8-hydroxyquinoline)aluminum derivatives soluble in a host polymer (pages 3006–3016)

      E. Shoji, K. Miyatake, A. R. Hlil, A. S. Hay, T. Maindron, V. Jousseaume, J. P. Dodelet, Y. Tao and M. D'Iorio

      Version of Record online: 12 AUG 2003 | DOI: 10.1002/pola.10883

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      Soluble tris(8-hydroxyquinoline)aluminum (AlQ3) derivatives have been synthesized and used in double spin-coated organic light-emitting devices of the type ITO/NPB-QP/A435 + 50 wt % soluble AlQ3 derivative/Mg, where NPB-QP is a hole-transporting polymer insoluble in toluene, the solvent for A435, a poly(aryl ether ketone) host polymer.

    10. Hemicyanine n-butyltriphenylborate salts as effective initiators of free-radical polymerization photoinitiated via photoinduced electron-transfer process (pages 3017–3026)

      Janina Kabatc, Beata Jędrzejewska and Jerzy Pączkowski

      Version of Record online: 19 AUG 2003 | DOI: 10.1002/pola.10886

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      Two different groups of hemicyanine n-butyltriphenylborate salts (HCBo) were synthesized and examined in order to verify the possibility of the Marcus equation application for the description of the kinetics of free-radical polymerization photoinitiated via the photoinduced electron transfer process (PET).

    11. Synthesis and monomer reactivity ratios of methyl methacrylate and 2-vinyl-4,4′-dimethylazlactone copolymers (pages 3027–3037)

      Lee G. Stanek, Steven M. Heilmann and William B. Gleason

      Version of Record online: 18 AUG 2003 | DOI: 10.1002/pola.10897

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      Copolymerization with functional monomers is an effective strategy for incorporating specific chemical functionalities into materials for specific applications. Homopolymers of methyl methacrylate (MMA) as well as MMA-based copolymers find wide applications, including uses as biomaterials. Copolymerization of the reactive monomer, 2-vinyl-4,4′-dimethylazlactone (VDMA), with MMA can introduce reactivity suitable for later facile attachment of biological macromolecules. Monomer reactivity ratios as reported for this system and this data can be used to produce tailored copolymers of known compositions and defined placement of VDMA in the copolymer chain. Such materials should be of wide utility for biotechnology and novel biomaterials.

    12. Initiator-fragment incorporation radical polymerization of divinylbenzene in the presence of glyoxylic oxime ether: Formation of soluble hyperbranched polymer (pages 3038–3047)

      Tsuneyuki Sato, Nobuyuki Sato, Makiko Seno and Tomohiro Hirano

      Version of Record online: 19 AUG 2003 | DOI: 10.1002/pola.10824

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      The copolymerization of divinylbenzene and ethylstyrene with dimethyl 2,2-azobisisobutyrate (MAIB) of high concentration at 70° and 80 °C in benzene in the presence of methyl benzyloxyiminoacetate (MBOIA) proceeded homogeneously and gave benzene-soluble copolymers. MAIB fragments as high as 30–40 mol % were incorporated into the copolymers through initiation and primary radical termination, on the basis of which the copolymerization was named the initiator-fragment incorporation radical polymerization. MBOIA (13–16 mol%) was also incorporated into the copolymers through an opening of the C[DOUBLE BOND]N bond. Results of gel permeation chromatography and multi-angle laser light scattering, transmission electron microscopy, and viscosity studies revealed that the copolymer was formed as a hyperbranched nanoparticle.

    13. Development of new dyeing photoinitiators based on benzylideneimidazopyridine dyes (pages 3048–3055)

      Ilona Pyszka, Zdzisław Kucybała and Jerzy Pączkowski

      Version of Record online: 14 AUG 2003 | DOI: 10.1002/pola.10891

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      A series of imidazopyridine dyes were prepared and tested as visible light-initiated initiator of free-radical polymerization.

    14. Synthesis and cationic photopolymerization of epoxy-functional siloxane monomers and oligomers (pages 3056–3073)

      Myoungsouk Jang and James V. Crivello

      Version of Record online: 20 AUG 2003 | DOI: 10.1002/pola.10890

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      A series of difunctional silicon-containing monomers were prepared with a novel method consisting of the monohydrosilation of an α,ω-difunctional Si[BOND]H-terminated siloxane with a vinyl-functional epoxide or oxetane followed by the dehydrodimerization of the resulting Si[BOND]H-functional intermediate. The reactivities of these new monomers and oligomers in photoinitiated cationic polymerization were examined with Fourier transform real-time infrared spectroscopy and optical pyrometry.

    15. Use of germanium initiators in ring-opening polymerization of L-lactide (pages 3074–3082)

      Anna Finne, Reema and Ann-Christine Albertsson

      Version of Record online: 14 AUG 2003 | DOI: 10.1002/pola.10887

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      Three different new germanium initiators with structure 1, 2, and 3 have been used for ring-opening polymerization of L-lactide. The initiator fragment was incorporated into the polymer during polymerization and the polymer ended up in an ABA block structure. All four GeOCH2 bonds participated in the polymerization and the occurrences of transesterification reactions during polymerization were low. The molecular weight distribution varied among the initiators from 1.2–1.4. The average molecular weights increased linearly with the monomer conversion and the molar mass of the achieved poly(L-lactide) were controlled by the monomer-to-initiator ratio.

    16. Synthesis and cleavage of core-labile poly(alkyl methacrylate) star polymers (pages 3083–3093)

      Lars Kilian, Zhen-He Wang and Timothy E. Long

      Version of Record online: 19 AUG 2003 | DOI: 10.1002/pola.10885

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      Core-cleavable star polymers were synthesized by the coupling of living anionic poly(alkyl methacrylate) arms with either dicumyl alcohol dimethacrylate (DCDMA) or 2,5-dimethyl-2,5-hexanediol dimethacrylate (DHDMA). High-molecular-weight star polymer cleavage under acidic conditions led to well-defined arm polymers with lower molecular weights. Thermogravimetric analysis of the star polymers demonstrated that the DCDMA and DHDMA star polymer cores also thermally degraded in the absence of acid.

    17. Triblock copolymers and pentablock terpolymers of n-hexyl isocyanate with styrene and isoprene: Synthesis, characterization, and thermal properties (pages 3094–3102)

      Aggelos Vazaios, Marinos Pitsikalis and Nikos Hadjichristidis

      Version of Record online: 19 AUG 2003 | DOI: 10.1002/pola.10882

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      Triblock copolymers and pentablock terpolymers of n-hexyl isocyanate (H), styrene (S), and isoprene (I) of the type HSH, HIH, HSISH, and HISIH were synthesized by anionic polymerization techniques and characterized by several methods. The thermal properties of the synthesized materials were examined by thermogravimetric analysis and differential scanning calorimetry. The middle block is styrene (S) or isoprene (I) homopolymers(triblock copolymers) ISI or SIS triblock copolymers(pentablock terpolymers).

    18. Covalently attached self-assembly of ultrathin films from hydroxy-containing porphyrin and diazoresin (pages 3103–3108)

      Yang Zhaohui and Cao Weixiao

      Version of Record online: 20 AUG 2003 | DOI: 10.1002/pola.10909

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      Ultrathin films from 5,10,15,20-tetrakis(4-hydroxyphenyl) porphyrin (HPP) and diazoresin (DR) via H bonding interaction have been fabricated by means of self-assembly (SA) technique. Under UV irradiation, the stability of the film was improved dramatically because of the formation of the crosslinking structure. Thus, the photoelectric conversion property of DR/HPP film can be measured directly with a normal photoelectric chemical cell using potassium chloride as the electrolyte. The maximum of anodic photocurrent was measured to be 1.7 μ Å for an eight bilayer DR/HPP film deposited on an indium–tin oxide glass electrode.

    19. Synthesis and polymerization of fluorinated monomers bearing a reactive lateral group. XIV. Radical copolymerization of vinylidene fluoride with methyl 1,1-dihydro-4,7-dioxaperfluoro-5,8-dimethyl non-1-enoate (pages 3109–3121)

      Bruno Ameduri and Gérard Bauduin

      Version of Record online: 20 AUG 2003 | DOI: 10.1002/pola.10908

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      The radical copolymerization in solution of vinylidene fluoride (VDF; or 1,1-difluoroethylene) with methyl 1,1-dihydro-4,7-dioxaperfluoro-5,8-dimethyl non-1-enoate (MDP) initiated by di-tert-butyl peroxide (DTBP) led to random copolymers. The assessment of the reactivity ratios (ri) of both comonomers showed a higher incorporation of MDP in the copolymers (rMDP = 2.41 ± 2.28 and rVDF = 0.38 ± 0.21 at 120 °C). The thermal properties of these fluorinated copolymers were also determined and showed that the copolymers were rather thermostable because the thermal degradation occurred at 280 °C.

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