Journal of Polymer Science Part A: Polymer Chemistry

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

15 December 2001

Volume 39, Issue 24

Pages 4189–4301

  1. Articles

    1. Top of page
    2. Articles
    3. NOTE
    4. Articles
    1. Stability of photocurable anhydrides: Methacrylic acid mixed anhydrides of nontoxic diacids (pages 4189–4195)

      Peter J. Tarcha, Lin Su, Tom Baker, Denton Langridge, Venkatram Shastri and Robert Langer

      Version of Record online: 25 OCT 2001 | DOI: 10.1002/pola.10073

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      Disproportionation of the liquid mixed anhydride dimethacrylic sebacic anhydride (m-SA) to methacrylic anhydride and polyanhydride oligomers, as well as vinylic polymerization, can occur spontaneously at room temperature. Dimethacrylic 1,3-bis(p-carboxyphenoxy) propane (m-CPP), being a solid, can also disproportionate, but the propensity to do so is lower than for m-SA. These events can be suppressed with free-radical inhibitors, and the inhibitor 2+3-t-butyl-4-methoxyphenol is a more effective stabilizer than 4-methoxyphenol at 20 °C.

    2. Photocrosslinking reaction of vinyl-functional polyphenylsilsesquioxane sensitized with aromatic bisazide compounds (pages 4196–4205)

      Naoki Yasuda, Shigeyuki Yamamoto, Yuji Wada and Shozo Yanagida

      Version of Record online: 25 OCT 2001 | DOI: 10.1002/pola.10065

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      The partially vinyl-substituted polyphenylsilsesquioxane containing an aromatic bisazide compound undergoes a photocrosslinking reaction with i-line (365-nm) light irradiation. The photoreaction of the photosensitive polymer system was investigated experimentally and theoretically mechanistically and can be applied as a novel photosensitive dielectric polymer to electronic devices.

    3. Vinyl polymerization with a binary system of p-chlorobenzenediazonium salt and sodium tetraphenylborate (pages 4206–4213)

      Tsuneyuki Sato, Toru Takahashi, Makiko Seno and Tomohiro Hirano

      Version of Record online: 26 OCT 2001 | DOI: 10.1002/pola.10071

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      A combined system of sodium tetraphenylborate (STPB) and p-chlorobenzenediazonium tetrafluoroborate (CDF) serves as an effective initiator at low temperatures for acrylate monomers such as methyl methacrylate (MMA), ethyl acrylate, and di-2-ethylhexyl itaconate. The polymerization rate (Rp) of MMA at 40 °C in acetone is given by Rp = k[STPB/CDF]0.5[MMA]1.6 ([STPB] = [CDF]). The polymerization shows a low overall activation energy of 60.3 kJ/mol. From the results of kinetic and spin trapping studies, it is concluded that STPB and CDF form a complex with a large stability constant that interacts with the monomer to generate p-chlorophenyl and phenyl radicals.

    4. Synthesis and chemical structural analysis of nitroxyl-radical-incorporated poly(acrylic acid/lactide/ϵ-caprolactone) copolymers (pages 4214–4226)

      Meidong Lang and Chih-Chang Chu

      Version of Record online: 29 OCT 2001 | DOI: 10.1002/pola.10030

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      The hydroxyl-terminated polylactide/ϵ-caprolactones (4, PBLC-OHs) were first synthesized by melt ring-opening copolymerization in the presence of benzyl alcohol and stannous octoate. PBLC-OHs were used as the precursor for the synthesis of double bond-fictionalized polylactide/ϵ-caprolactones (6, PBLC-Mas) by reacting the hydroxyl end groups of PBLC-OH with maleic anhydride in melt at 130 °C. Acrylic acid/lactide/ϵ-caprolactone graft copolymers (8, PBLCAs) were then successfully carried out by the radical copolymerization of acrylic acid and PBLC-Ma initiated by azobisisobutyronitrile. Finally, nitroxyl radicals [4-amino-2,2,6,6-tetramethylpiperidine-1-oxy (TAM)] were incorporated into the carboxylic acid sites of the acrylic acid/lactide/ϵ-caprolactone copolymer (10, TAM-PBLCA) by reacting TAM with PBLCA in the presence of N,N′-carbonyl diimidazole.

    5. Effect of the structural parameters of a series of fluoromonoacrylates on the surface properties of cured films (pages 4227–4235)

      B. Ameduri, R. Bongiovanni, V. Lombardi, A. Pollicino, A. Priola and A. Recca

      Version of Record online: 26 OCT 2001 | DOI: 10.1002/pola.10072

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      Fluorinated acrylates were synthesized and used as comonomers in the photopolymerization of acrylic systems. Transparent films were obtained, showing changes in the surface properties. With contact-angle and X-ray photoelectron spectroscopy analyses, the relationship between the structure of the monomers and the surface properties of the UV-cured films was investigated: the wettability decreased, depending on not only the fluorine content but also the structure of the monomer. In the figure, the wettability of UV-cured films in the presence of perfluorooctyl acrylates with different structures is shown: (♦) C8F17(CH2)2OCOCH[DOUBLE BOND] CH2, (▪) C8F17(CH2)3OCOCH[DOUBLE BOND]CH2, (▵) C8F17(CH2)2 SCH2CH2 OCOCH[DOUBLE BOND]CH2, and (×) C8F17(CH2)11OCOCH[DOUBLE BOND]CH2.

    6. Catalysis of poly(urethane imidine) copolymer formation from amine-blocked isocyanate and bisphthalide (pages 4236–4242)

      N. Padmanabha Iyer, T. Philip Gnanarajan and Ganga Radhakrishnan

      Version of Record online: 29 OCT 2001 | DOI: 10.1002/pola.10077

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      Alkali metal alkoxides and phenoxides catalyzed the reaction between N-methylaniline-blocked polyurethane prepolymer and bisphthalide. With tin catalysts, the imidinization was dependent on the deblocking of the blocked prepolymer, but it was independent of deblocking with amine catalysts. With the incorporation of imidine moieties, the thermal stability of polyurethane increased significantly.

    7. Metallocene derivatives as active supports of zirconium-based catalysts for ethene polymerization (pages 4243–4248)

      Stefano Mortara, Daniele Fregonese, Silvano Bresadola, Rita Boaretto and Silvana Sostero

      Version of Record online: 29 OCT 2001 | DOI: 10.1002/pola.10076

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      Cyclopentadienyl magnesium chloride and its derivatives are proposed as original and interesting supports for heterogenizing zirconium metallocene catalysts active in ethene polymerization. In comparison with catalysts obtained with the conventional method of immobilization, the reported heterogenized catalysts have important advantages, such as a lack of metallorganic active complex leaching and good morphology control of the growing polymer.

  2. NOTE

    1. Top of page
    2. Articles
    3. NOTE
    4. Articles
    1. Highly stabilized nanostructures from poly(L-lactide)-block-poly(oxyethylene) having a photoreactive end functionality (pages 4249–4254)

      Tomoko Fujiwara, Tadahisa Iwata and Yoshiharu Kimura

      Version of Record online: 29 OCT 2001 | DOI: 10.1002/pola.10080

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      An AB diblock copolymer consisting of poly(L-lactide) and poly(oxyethylene) monocinnamate (PEG-C) was synthesized and dispersed in an aqueous medium to prepare its core/shell particles. These particles were cast on a flat mica surface and heat-treated to induce a morphological change into nanobands. UV irradiation of the resultant nanobands led to crosslinking of the cinnamate groups in the PEG shell with stabilization of the nanobands. The self-organized macromolecular system thus obtained was a new nanoarchitecture of synthetic polymers.

  3. Articles

    1. Top of page
    2. Articles
    3. NOTE
    4. Articles
    1. Synthesis and characterization of polyisocyanides derived from alanine and glycine dipeptides (pages 4255–4264)

      Jeroen J. L. M. Cornelissen, W. Sander Graswinckel, P. J. H. M. Adams, Gerda H. Nachtegaal, Arno P. M. Kentgens, Nico A. J. M. Sommerdijk and Roeland J. M. Nolte

      Version of Record online: 1 NOV 2001 | DOI: 10.1002/pola.10083

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      Optically pure dipeptides based on alanine and glycine have been equipped with an isocyano function and were subsequently polymerized using a Ni(II) catalyst. The side chains of these polymers are connected by well-defined arrays of intramolecular hydrogen bonds, giving rise to rigid, well-defined polymer architectures that can be visualized using atomic force microscopy.

    2. Polymerization of acrylamide photoinitiated by tris(2,2′-bipyridine)ruthenium(II)–amine in aqueous solution: Effect of the amine structure (pages 4265–4273)

      Claudia R. Rivarola, Sonia G. Bertolotti and Carlos M. Previtali

      Version of Record online: 1 NOV 2001 | DOI: 10.1002/pola.10084

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      The photopolymerization of acrylamide (AA) initiated by the metallic complex tris(2,2′-bipyridine)ruthenium(II) [Ru(bpy)32+] in the presence of aliphatic and aromatics amines as co-initiators was investigated in aqueous solution. Laser-flash photolysis experiments show the presence of the reduced form of the complex, Ru(bpy)3+1, for all the amines investigated. A mechanism involving an electron-transfer process from the Ru(bpy)3+1 to AA is proposed.

    3. Organic–inorganic hybrid networks by the sol–gel process and subsequent photopolymerization (pages 4274–4282)

      Ekkehard Müh, Markus Stieger, Joachim E. Klee, Holger Frey and Rolf Mülhaupt

      Version of Record online: 1 NOV 2001 | DOI: 10.1002/pola.10079

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      Organic–inorganic hybrid materials were prepared by a convenient two-step curing procedure based on sol–gel condensation and subsequent photopolymerization. Novel bismethacrylate-based hybrid monomers with pendant, condensable alkoxysilane groups were prepared by Michael addition. The formation of inorganic networks by sol–gel condensation of the alkoxysilane groups in the presence of aqueous methacrylic acid was monitored with rheological measurements. Subsequent photopolymerization led to organic–inorganic hybrid networks and low volume shrinkage, depending on the molecular weight of the hybrid monomer. Highly filled composite materials with glass filler fractions greater than 75% showed attractive mechanical properties with Young's moduli of 2700–6200 MPa.

    4. Sequential poly(ester amide)s based on glycine, diols, and dicarboxylic acids: Thermal polyesterification versus interfacial polyamidation. Characterization of polymers containing stiff units (pages 4283–4293)

      L. Asín, E. Armelin, J. Montané, A. Rodríguez-Galán and J. Puiggalí

      Version of Record online: 1 NOV 2001 | DOI: 10.1002/pola.10082

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      Sequential poly(ester amide)s derived from glycine were synthesized by a two-step method involving a final thermal polyesterification. Molecular weights were in general higher than those obtained with the previously reported synthesis on the basis of interfacial polyamidation. Polymers with stiff units like oxaloyl (PGnG0) or terephthaloyl (PGnGT) residues were thermally characterized and their degradability studied by using different types of enzymes. Polymers containing short diols are degradable in papain solutions, the degradation rate being higher for oxalic derivatives.

    5. Atom transfer radical polymerization of n-butyl acrylate from silica nanoparticles (pages 4294–4301)

      G. Carrot, S. Diamanti, M. Manuszak, B. Charleux and J.-P. Vairon

      Version of Record online: 1 NOV 2001 | DOI: 10.1002/pola.10085

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      The synthesis of well-defined nanoparticle films and materials is often plagued by particle aggregation. One solution to this problem is the grafting of polymer chains to the nanoparticles. The “grafting from” method combined with atom transfer radical polymerization can be beneficially applied to the synthesis of hybrid inorganic/organic nanocomposites. The polymerization from silica nanoparticles where initiator molecules are immobilized by grafting at the particle surface is presented and compared with equivalent solution polymerization in the same conditions.

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