Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 43 Issue 14

15 July 2005

Volume 43, Issue 14

Pages 2951–3187

  1. Highlights

    1. Top of page
    2. Highlights
    3. Articles
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      From thermoplastic elastomers to designed biomaterials (pages 2951–2963)

      Joseph P. Kennedy

      Article first published online: 1 JUN 2005 | DOI: 10.1002/pola.20844

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      Select milestones on the road from polyisobutylene-based thermoplastic elastomers to designed proof-of-concept biomaterials include toughened bone cements, injectable intervertebral discs, drug delivery depots, artificial blood vessels, and amphiphilic membranes for the immunoisolation of living pancreatic tissue. The sketch outlines the cocrosslinking of a stimuli-responsive smart amphiphilic conetwork from hydrophilic and hydrophobic chains.

  2. Articles

    1. Top of page
    2. Highlights
    3. Articles
    1. Directly copolymerized poly(arylene sulfide sulfone) disulfonated copolymers for PEM-based fuel cell systems. I. Synthesis and characterization (pages 2964–2976)

      K. B. Wiles, F. Wang and J. E. McGrath

      Article first published online: 2 JUN 2005 | DOI: 10.1002/pola.20744

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      Direct aromatic nucleophilic substitution polycondensations of disodium 3,3′-disulfonate-4,4′-difluorodiphenylsulfone (SDFDPS), 4,4′-difluorodiphenylsulfone (DFDPS) (or their chlorinated analogs, SDCDPS, DCDPS), and 4,4′-thiobisbenzenthiol (TBBT) in the presence of potassium carbonate were investigated. High molecular weight disulfonated poly-(aryelene thioether sulfone) (PATS) copolymers were easily obtained using the SDFDPS monomers, but in general, slower rates and lower molecular weights were obtained using the analogous chlorinated monomers. The degrees of disulfonation (20–50%) were controlled by varying the ratio of disulfonated to unsulfonated comonomers. Proton NMR, infrared spectroscopy, and ion exchange capacity experiments successfully characterized the copolymer structure. Morphological studies using AFM phase imaging coupled with water uptake studies indicated an increase in connectivity of ionic domains from the low disulfonated copolymers to levels of full connectivity for the 40 mol % copolymer.

    2. Preparation of poly(ethylene oxide)-block-poly(isoprene) by nitroxide-mediated free radical polymerization from PEO macroinitiators (pages 2977–2984)

      Jakub K. Wegrzyn, Tim Stephan, Ryan Lau and Robert B. Grubbs

      Article first published online: 1 JUN 2005 | DOI: 10.1002/pola.20756

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      Amphiphilic poly(ethylene oxide)-block-poly(isoprene) (PEO-b-PI) diblock copolymers were prepared by nitroxide-mediated polymerization of isoprene from alkoxyamine-terminal poly(ethylene oxide) (PEO). Micellar aggregates of PEO-b-PI in aqueous solution were crosslinked by treatment with a water-soluble redox initiating system, and persistent micellar structures were observed in the dry state by AFM.

    3. Synthesis and characterization of novel biodegradable epoxy-modified polyurethane elastomers (pages 2985–2996)

      Hamid Yeganeh, Moslem Mansour Lakouraj and Sadegh Jamshidi

      Article first published online: 2 JUN 2005 | DOI: 10.1002/pola.20789

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      Biodegradable polyurethane elastomers with the potential for applications in medical implants were synthesized from the reaction of epoxy-terminated polyurethane prepolymers with a diamine curing agent. A structure–property relationship was established for the synthesized network via the evaluation of the physical and mechanical properties, and the effects of two main factors, the crystallinity and crosslink density, on the physical properties as well as the degradability of the final networks were studied.

    4. Synthesis of poly(isobutyl-co-2,2,2-trifluoroethyl methacrylate) with 5,10,15,20-tetraphenylporphinato platinum(II) moiety as an oxygen-sensing dye for pressure-sensitive paint (pages 2997–3006)

      Makoto Obata, Yurie Tanaka, Naoko Araki, Shiho Hirohara, Shigenobu Yano, Kazunori Mitsuo, Keisuke Asai, Masafumi Harada, Toyoji Kakuchi and Chikara Ohtsuki

      Article first published online: 1 JUN 2005 | DOI: 10.1002/pola.20776

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      A novel fluorinated polymethacrylate with 5,10,15,20-tetraphenylporphinato platinum(II) (dye-pendent polymer) was synthesized for PSP applications. The oxygen-sensing property was examined on a dye-pendent polymer film and a dye-mixed polymer film. Although the dye-mixed polymer film showed a remarkable deviation from a single Stern–Volmer relation, the novel dye-pendent polymer showed excellent linearity in the Stern–Volmer plot.

    5. Pt-catalyzed chemical modification of α,ω-bis(hydrido)polydimethylsiloxanes and copoly(methylhydridosiloxane/dimethylsiloxane) with vinylheptaphenylcyclotetrasiloxane (pages 3007–3017)

      Thomas M. Gädda and William P. Weber

      Article first published online: 2 JUN 2005 | DOI: 10.1002/pola.20778

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      A series of α,ω-bis(hydrido)polydimethylsiloxanes and copoly(methylhydridosiloxane/dimethylsiloxane) were chemically modified by the attachment of vinylheptaphenylcyclotetrasiloxane moieties. The molecular weights and thermal properties were characterized and compared with those of polydimethylsiloxane. The crystallization behavior was significantly altered by the modification. A considerable increase in the bulk viscosity was measured after the modification.

    6. Synthesis and characterization of organosoluble ditrifluoromethylated aromatic polyimides (pages 3018–3029)

      Baijun Liu, Wei Hu, Toshihiko Matsumoto, Zhenhua Jiang and Shinji Ando

      Article first published online: 3 JUN 2005 | DOI: 10.1002/pola.20770

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      A series of ditrifluoromethylated aromatic polyimides derived from two novel diamines were prepared and characterized. Their thermal properties, solubility, mechanical properties, optical properties and dielectric constants were investigated.

    7. Lipase-catalyzed ring-opening polymerization of 6(S)-methyl-morpholine-2,5-dione (pages 3030–3039)

      Yakai Feng, Doris Klee and Hartwig Höcker

      Article first published online: 1 JUN 2005 | DOI: 10.1002/pola.20775

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      The enzymatic ring-opening polymerization of 6(S)-methyl-morpholine-2,5-dione in the bulk was investigated by using the lipase PPL as a catalyst. During the polymerization of 6(S)-methyl-morpholine-2,5-dione racemization of the lactic acid moiety took place. Enzymatic polymerization produced polydesipeptides with a carboxylic acid group at one end and a hydroxyl group at the other one.

    8. Highly conductive soluble terpolymers of aniline, toluidine, and o-aminobenzoic acid/m-aminobenzenesulfonic acid (pages 3040–3048)

      P. Savitha and D. N. Sathyanarayana

      Article first published online: 3 JUN 2005 | DOI: 10.1002/pola.20794

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      Two series of terpolymers, one of aniline, o-/m-toluidine, and o-aminobenzoic acid and the other of aniline, o-/m-toluidine, and m-aminobenzenesulfonic acid, have been synthesized with emulsion polymerization. The terpolymers exhibit high conductivity (∼1 S cm−1) and possess higher thermal stability than polyaniline. Absorption spectra suggest that, in the terpolymers containing m-aminobenzenesulfonic acid, the extent of protonation is higher than that in the terpolymers containing o-aminobenzoic acid.

    9. Preparation and characterization of the chromatographic properties of ethylene glycol dimethacrylate/divinylbenzene polymeric microspheres (pages 3049–3058)

      Małgorzata Maciejewska, Joanna Osypiuk and Barbara Gawdzik

      Article first published online: 3 JUN 2005 | DOI: 10.1002/pola.20780

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      The preparation of porous ethylene glycol dimethacrylate/divinylbenzene polymeric microspheres is presented. Employing suspension–emulsion polymerization allowed microspheres to be obtained with diameters of 2–20 μm. These materials were investigated as column packings for high-performance liquid chromatography. Their porous structures in both the dry and wet states were also studied.

    10. Synthesis of carbohydrate-linked poly(polyoxometalate) poly(amido)amine dendrimers (pages 3059–3066)

      Joel R. Morgan and Mary J. Cloninger

      Article first published online: 3 JUN 2005 | DOI: 10.1002/pola.20799

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      Mannose-functionalized and ethoxyethanol-functionalized poly(amido)amine (PAMAM) dendrimers bound multiple vanadate-substituted polyoxotungstate Wells–Dawson-type polyoxometalates (POMs). Dendrimers incorporating 10–30 POMs were characterized with NMR, transmission electron microscopy, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry techniques. The number of metal clusters per dendrimer molecule varied according to the dendrimer generation and the nature of the surface functional groups. Efforts aimed at using the poly(polyoxometalate) dendrimers as oxidation catalysts are also described.

    11. Synthesis and characterization of side-chain liquid-crystalline polymers and study of their role in the crystallization of high-density polyethylene (pages 3067–3078)

      Wen-Qiang Qiao, Xiao-Dong Fan, Jie Kong, Yun-Chuan Xie, Qing-Fa Si, Sheng-Jie Wang and Yu-Yang Liu

      Article first published online: 2 JUN 2005 | DOI: 10.1002/pola.20793

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      To investigate the potential of side-chain liquid-crystalline polymers (SCLCPs) as nucleating agents for semicrystalline polymers, four SCLCPs were designed, prepared, and characterized. One of the four SCLCPs, P4, was used as a nucleating agent for high-density polyethylene (HDPE). The nucleating effect of P4 was investigated with differential scanning calorimetry and polarized optical microscopy, with the common small-molecule nucleating agent 1,3:2,4-dibenzylidenesorbitol (DBS) as a reference material. The results showed that P4 could effectively increase both the crystallization temperature and rate and, at the same time, raise the crystallinity for HDPE. In comparison with DBS, P4 was more efficient.

    12. Synthesis, photophysics, structure-tunable photoluminescence, and electrochemical properties of soluble poly(p-phenylenevinylene)-based polymers with adjacent 1,3,4-oxadiazoles in the backbone (pages 3079–3090)

      John A. Mikroyannidis, Helena Hlídková, Drahomír Výprachtický and Věra Cimrová

      Article first published online: 7 JUN 2005 | DOI: 10.1002/pola.20771

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      Three new poly(p-phenylenevinylene)-based polymers containing two adjacent oxadiazoles in the main chain per repeat unit and a single, double, or triple bond between the oxadiazoles were synthesized. The polymers behaved as strongly photoluminescent materials. The color of the emissive light in both the solid state and the solution could be tuned from ultraviolet to green by a change in the nature of the bond between the oxadiazole rings.

    13. Synthesis and characterization of poly(ethylene glycol) polymers functionalized by terminal tributyltin carboxylate moieties (pages 3091–3104)

      Luigi Angiolini, Daniele Caretti, Laura Mazzocchetti, Elisabetta Salatelli, Rudolph Willem and Monique Biesemans

      Article first published online: 7 JUN 2005 | DOI: 10.1002/pola.20790

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      Novel polymeric derivatives bearing tributyltin carboxylate moieties as end groups have been prepared from properly functionalized poly(ethylene glycol)s of various average molecular weights. The related low-molecular-weight derivatives have also been synthesized with the aim of investigating the influence of the polymeric chain on tin properties. Sn NMR and Fourier transform infrared investigations, both in solution and in the solid state, have established the type and nature of the coordination at tin, whereas thermal analysis has indicated a distinct behavior of the low-molecular-weight model compounds with respect to the polymeric ones, as confirmed by X-ray diffraction patterns.

    14. Novel photocurable monomers: The synthesis of difunctional vinyl ethers with a phosphonate group and difunctional 1-propenyl ethers with a phosphonate group and their photoinitiated cationic polymerization (pages 3105–3115)

      Shouji Minegishi, Tetsurou Otsuka, Atsushi Kameyama and Tadatomi Nishikubo

      Article first published online: 2 JUN 2005 | DOI: 10.1002/pola.20779

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      Phosphorus-containing vinyl ether monomers and 1-propenyl ether monomers were prepared by the regioselective addition reaction of glycidyl vinyl ether or 1-propenyl glycidyl ether with diaryl phosphonates with quaternary onium salts as catalysts. Photoinitiated cationic polymerizations of the resulting phosphorus-containing vinyl ether monomers and 1-propenyl ether monomers were investigated with photoinitiators. The polymerization of vinyl ether groups and 1-propenyl ether groups of the obtained monomers proceeded very smoothly with a sulfonium-type cationic photoinitiator, bis[4-(diphenylsulfonio)phenyl]sulfide-bis(hexafluorophosphate), upon UV irradiation.

    15. Effect of aniline formaldehyde resin on the conjugation length and structure of doped polyaniline: Spectral studies (pages 3116–3125)

      Ko-Shan Ho, Tar-Hwa Hsieh, Chung-Wen Kuo, Swu-Wen Lee, Jong-Jing Lin and Ying-Jie Huang

      Article first published online: 7 JUN 2005 | DOI: 10.1002/pola.20796

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      X-ray diffraction patterns of DBSA (n-dodecylbenzene sulfate)-doped polyaniline [PANI(DBSA)0.5]/DBSA-complexed aniline formaldehyde [AF(DBSA)1.0] showed that the layered structure of PANI(DBSA)0.5 was still present but became shorter in the polyblend because of the presence of AF(DBSA)1.0. Solid-state 13C NMR spectra revealed that the reverse doping effect came from the interaction of alkyl groups between n-dodecylbenzene sulfonic acid (HDBSA), complexed DBSA, and dopant DBSAs.

    16. Syntheses and electroluminescence properties of conjugated poly(p-phenylene vinylene) derivatives bearing dendritic pendants (pages 3126–3140)

      Rupei Tang, Yutao Chuai, Caixia Cheng, Fu Xi and Dechun Zou

      Article first published online: 7 JUN 2005 | DOI: 10.1002/pola.20798

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      A series of new poly(p-phenylene vinylene) (PPV) derivatives with different dendritic pendants were successfully synthesized according to the Gilch route. The resulting polymers possessed excellent solubility in common organic solvents, good thermal stability, and high molecular weights. In solution, the polymers emitted green light with relatively high photoluminescence quantum yields (0.43–0.65). Double-layer light-emitting diodes with the configuration of indium tin oxide/polymer/tris(8-hydroxyquinoline) aluminum/Mg:Ag/Ag devices were fabricated, and they emitted green-yellow light. The turn-on voltages of the polymers were low compared with those of other PPV dendrimers. The synthesized PPV derivatives may have potential applications for large-area flat-panel displays.

    17. Controlled/living polymerization of methacrylamide in aqueous media via the RAFT process (pages 3141–3152)

      Yulia A. Vasilieva, Charles W. Scales, David B. Thomas, Ryan G. Ezell, Andrew B. Lowe, Neil Ayres and Charles L. McCormick

      Article first published online: 7 JUN 2005 | DOI: 10.1002/pola.20786

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      The polymerization of methacrylamide (MAM) was performed in aqueous media via reversible addition fragmentation chain transfer (RAFT) polymerization with the dithiobenzoate chain-transfer agent (CTA) 4-cyanopentanoic acid dithiobenzoate. The polymerization in unbuffered water at 70 °C was controlled for the first 3 h, after which the molecular weight distribution broadened and a substantial deviation of the experimental from the theoretical molecular weight occurred, presumably because of a loss of CTA functionality at longer polymerization times. Conducting the polymerization in an acidic buffer afforded a well-defined homopolymer [number-average molecular weight (Mn) = 23,800 g/mol, weight-average molecular weight/number-average molecular weight (Mw/Mn) = 1.08] up to 98% conversion. To demonstrate the controlled/living nature of the system, a block copolymer of MAM and acrylamide was successfully prepared (Mn = 33,800 g/mol, Mw/Mn = 1.25) from a polymethacrylamide macro-CTA.

    18. Synthesis and characterization of novel fluoride-releasing monomers. II. Dimethacrylates containing bis(aminodiacetic acid) and their ternary zirconium fluoride complexes (pages 3153–3166)

      Xiaoming Xu, Xingzhe Ding, Long Ling and John O. Burgess

      Article first published online: 7 JUN 2005 | DOI: 10.1002/pola.20787

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      Novel dimethacrylate monomers containing bis(aminodiacetic acid) and characterized by electrospray mass spectrometry (ESMS), 1H NMR, and 13C NMR. The most stable ternary zirconium fluoride complex was in the form of [LZrF], where H4L is the monomer containing bis(aminodiacetic acid) without additional hydroxyl groups. The fluoride release, fluoride recharge, compressive strength, and flexure strength were tested on the experimental dental composite containing 13.7 wt % synthesized monomer and three commercial flowable dental composites. The results showed that the experimental composite has significantly higher fluoride release and recharge capabilities than the commercial materials. The compressive strength was comparable to that of the commercial materials.

    19. Synthesis, characterization, and metal complexes of polyacetylenes with pendant 2,2′-bipyridyl groups (pages 3167–3177)

      José Vicente, Juan Gil-Rubio and Natalia Barquero

      Article first published online: 8 JUN 2005 | DOI: 10.1002/pola.20816

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      The synthesis and characterization of the first stereoregular cis–transoidal polyacetylene containing uncoordinated bipyridine substituents is reported. With this polymer, metallopolymers containing pendant [Ru(bpy)3]2+ and [Mo(bpy)(CO)4] complexes were obtained. In addition, random and block copolymers containing both bipyridine and aryl substituents were prepared.

    20. Development of an efficient route to hyperbranched poly(arylene ether sulfone)s (pages 3178–3187)

      Patrick Himmelberg and Eric Fossum

      Article first published online: 7 JUN 2005 | DOI: 10.1002/pola.20817

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      An efficient synthesis of hyperbranched poly(arylene ether sulfone)s (HB PAES) has been developed. The synthesis of 3,5-difluoro-4′-hydroxydiphenyl sulfone (4) requires a simple two-step process that affords multigram quantities of 4. The polymerization of 4 provides HB PAES samples with molecular weights of 3400–8400 Da.