Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 42 Issue 15

1 August 2004

Volume 42, Issue 15

Pages 3655–3909

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      The discovery of two kinds of ion pairs (pages 3655–3667)

      Johannes Smid

      Article first published online: 28 JUN 2004 | DOI: 10.1002/pola.20260

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      The discovery of tight and loose ion pairs in solutions of carbanion salts, and its ramifications in understanding the mechanism of living anionic polymerization are reviewed. The optical absorption spectrum of tight and DMSO-separated ion pairs of fluorenyl lithium in mixtures of dioxane and DMSO is shown.

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    1. Characterization of molecularly imprinted polymers employing crosslinkers with nonsymmetric polymerizable groups (pages 3668–3675)

      Martha Sibrian-Vazquez and David A. Spivak

      Article first published online: 17 JUN 2004 | DOI: 10.1002/pola.20186

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      Molecularly imprinted polymers (MIPs) that incorporate crosslinkers with two different polymerizable moieties show improved binding and selectivity. The characterization of these new MIP materials suggests a new mechanism for this class of polymers that gives rise to morphological factors that can account for the improved binding properties.

    2. Preparation and properties of alkoxy(methyl)silsesquioxanes as coating agents (pages 3676–3684)

      Takahiro Gunji, Yasuhito Iizuka, Koji Arimitsu and Yoshimoto Abe

      Article first published online: 17 JUN 2004 | DOI: 10.1002/pola.20233

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      Polysilsesquioxanes were prepared through the acid-catalyzed hydrolytic polycondensation of trialkoxy(methyl)silanes and subjected to dip coating followed by heat treatment. The adhesion and hardness of the coating films increased with increases in the heating time and heat-treatment temperature. The surface electric resistance increased with the heat-treatment temperature up to 500 °C.

    3. Photocrosslinking system using multifunctional epoxy crosslinkers having thermally degradable properties (pages 3685–3696)

      Haruyuki Okamura, Kazuo Shin, Masahiro Tsunooka and Masamitsu Shirai

      Article first published online: 17 JUN 2004 | DOI: 10.1002/pola.20232

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      A novel thermally degradable photocrosslinking system was investigated. Difunctional and trifunctional epoxides with tertiary ester linkages were synthesized. When blended films of epoxides and poly(vinyl phenol) or epoxides and poly(methacrylic acid-co-ethyl methacrylate) with a photoacid generator were irradiated and then baked at relatively low temperatures (<100 °C), the films became insoluble in solvents. The insoluble fractions of the blended films containing the trifunctional epoxide were higher than the fractions of the films containing the difunctional epoxide. The crosslinked films became soluble after baking at relatively high temperatures (>120 °C).

    4. Synthesis of alkaline-developable, photosensitive hyperbranched polyimides through the reaction of carboxylic acid dianhydrides and trisamines (pages 3697–3707)

      Shohei Makita, Hiroto Kudo and Tadatomi Nishikubo

      Article first published online: 17 JUN 2004 | DOI: 10.1002/pola.20239

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      The synthesis and characterization of alkaline—developable, photosensitive hyperbranched polyimide HBPI(TAPE-DSDA)-MA-CA containing methacryloyl and carboxylic acid groups at the ends were investigated. A resist composed of HBPI(TAPE-DSDA)-MA-CA, trimethylpropane triacrylate, and Irgacure 907 as a photoinitiator achieved a resolution of a 55-μm line-and-space pattern by UV irradiation (1000 mJ/cm2).

    5. Synthesis and characterization of secondary-amine-functional microparticles (pages 3708–3719)

      E. Banu Altintaş and Soner Kiliç

      Article first published online: 18 JUN 2004 | DOI: 10.1002/pola.20268

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      Secondary amine functional microparticles in the particle size range of 50–250 μm were synthesized by suspension polymerization. The microparticles containing 5–50 weight percent amine functional monomer were prepared using styrene and divinylbenzene as comonomers in the presence of aluminum sulfate or aluminum sulfate/sodium dodecylsulfate stabilizers. The effects of the polymerization parameters on the particle size, particle size distribution, and swelling ratio also were investigated.

    6. Ionic organic/inorganic materials. II. New linear and crosslinked poly(ethylene oxide)-based ionomers by quaternization with chloroalkyl-functionalized siloxanes (pages 3720–3728)

      Maria Cazacu, Luminita Ghimici and Ecaterina Stela Dragan

      Article first published online: 21 JUN 2004 | DOI: 10.1002/pola.20267

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      Siloxane-modified cationic ionomers were synthesized through the quaternization reaction of a poly(ethylene glycol)-based polymer containing tertiary amine groups in the chain with chloroalkyl-functionalized siloxanes. Linear or crosslinked structures were obtained, depending on the functionality of the siloxane (R): a chloroalkyl mono- or polyfunctionalized siloxane was used.

    7. Gel formation in cationic polymerization of divinyl ethers. III. Effect of oligooxyethylene chain versus oligomethylene chain as central spacer units (pages 3729–3738)

      Tamotsu Hashimoto, Tomonori Nakamura, Sachi Tanahashi and Toshiyuki Kodaira

      Article first published online: 21 JUN 2004 | DOI: 10.1002/pola.20229

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      Cationic polymerizations of two series of divinyl ethers were carried out with the hydrogen chloride/zinc chloride (HCl/ZnCl2) initiating system in CH2Cl2 at −30 °C ([Monomer]0 = 0.15 M) to clarify the effects of their central spacer chain structure on their crosslinking polymerization behavior. One series of the monomers involves divinyl ethers with an oligooxyethylene chain: O-3, O-4, O-5, O-6, and O-8, and the other series includes divinyl ethers with an oligomethylene chain: C-4, C-6, and C-8. On the basis of comparison of the polymerization behavior of the two series, it was proposed that the oligooxyethylene chains adjacent to the pendant unreacted vinyl ether groups of the polymers may solvate intramolecularly with the carbocationic active center to accelerate frequent occurrence of intramolecular crosslinking reactions.

    8. Synthesis and chemical modification of hyperbranched polyethers with terminal hydroxy groups by the anionic ring-opening polymerization of 3-alkyl-3-hydroxymethyl oxetanes (pages 3739–3750)

      Ayako Morita, Hiroto Kudo and Tadatomi Nishikubo

      Article first published online: 21 JUN 2004 | DOI: 10.1002/pola.20236

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      The anionic ring-opening polymerization of oxetane containing hydroxy groups was examined with potassium tert-butoxide as an initiator in the presence of 18-crown-6-ether in N-methylpyrrolidinone at 180 °C; it yielded a corresponding multifunctional hyperbranched polymer, poly(3-ethyl-3-hydroxymethyloxetane), in a good yield. Poly(3-ethyl-3-hydroxymethyloxetane) had an oxetane moiety and many hydroxy groups at the ends. The cationic polymerization of a poly(3-ethyl-3-hydroxymethyloxetane) derivative was performed with boron trifluoride etherate as an initiator and was followed by alkaline hydrolysis; this yielded a new branched polymer, poly(hyperbranched polyether), with many pendant hydroxy groups.

    9. Hyperbranched polyesters of 3,5-diacetoxybenzoic acid: A reinvestigation (pages 3751–3760)

      Hans R. Kricheldorf, Radka Hobzova, Gert Schwarz and Claus-Ludolf Schultz

      Article first published online: 22 JUN 2004 | DOI: 10.1002/pola.20217

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      3,5-Bis-acetoxybenzoic acid and its trimethylsilylester were polycondensed at temperatures above 220 °C with variation of time and catalyst. The matrix-assisted laser desorption/ionization time-of-flight mass spectra revealed the formation of hyperbranched polyesters with cyclic core and loss of acetate groups by thermal elimination.

    10. Zirconocene-catalyzed copolymerization of methyl methacrylate with other methacrylate monomers (pages 3761–3774)

      Giorgos Karanikolopoulos, Christos Batis, Marinos Pitsikalis and Nikos Hadjichristidis

      Article first published online: 22 JUN 2004 | DOI: 10.1002/pola.20191

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      Statistical copolymers of methyl methacrylate, MMA, with n-butyl-, s-butyl-, t-butyl-, n-hexyl-, decyl-, stearyl-, allyl-, trimethylsilyl- and trimethylsilyoxyethylmethacrylate were prepared by zirconocene-catalyzed copolymerization. The reactivity ratios of MMA copolymers with butyl-, hexyl-, and stearyl methacrylate were estimated using the Finemann-Ross, the inverted Finemann-Ross and the Kelen-Tüdos graphical methods. The thermal properties of the copolymers were studied by differential scanning calorimetry.

    11. Living ring-opening polymerization of lactides catalyzed by guanidinium acetate (pages 3775–3781)

      Hong Li, Chenhong Wang, Jin Yue, Xiaona Zhao and Feng Bai

      Article first published online: 22 JUN 2004 | DOI: 10.1002/pola.20275

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      Hexabutyl guanidinium acetate HBG · OAc was synthesized and successfully used as an initiator for ring-opening polymerization of lactides. Polymerization in bulk (120 °C, 18h) produced polylactides with moderate molecular weights (Mn 2.0 × 104) and very narrow molecular weight distributions (polydispersity index 1.07–1.12). The polymerization mechanism was postulated to follow the coordination-insertion mechanism on the basis of additive effect of the polymerization and 1H NMR characterization of microstructure of the product polymers.

    12. Influence of lanthanide triflate compounds on formation of networks from DGEBA and γ-butyrolactone (pages 3782–3791)

      Cristina Mas, Ana Mantecón, Angels Serra, Xavier Ramis and Josep Maria Salla

      Article first published online: 22 JUN 2004 | DOI: 10.1002/pola.20180

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      The diglycidylether of bisphenol A was cured with γ-butyrolactone and lanthanide triflates as catalyst. The evolution of the four elemental processes occurring during curing was monitored by FTIR. The greatest differences among lanthanides are in the oxophilicity, coordination ability and Lewis acidity. Differences in the reactivity of the systems have been related to the different Lewis acidity of the initiators. The evolution of the contraction during curing using different lanthanide triflates was monitored by TMA.

    13. Guest–host chemistry with dendrimers: Stable polymer assemblies by rational design (pages 3792–3799)

      Michael Pittelkow, Jørn B. Christensen and E. W. Meijer

      Article first published online: 23 JUN 2004 | DOI: 10.1002/pola.20276

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      A new type of guest has been designed for exo-type supramolecular functionalization of adamantyl-urea-terminated poly(propylene imine) dendrimers. The new type of guest–motif features a uriedo methane sulfonic acid moiety that binds very selectively to the surface of the dendrimer forming well-defined complexes. The guest–host properties have been examined on a generation 5 adamantyl-urea-functionalized poly(propylene imine) dendrimer capable of binding 32 guest molecules and on a model host molecule only binding one guest molecule. Competition experiments with guests bearing a carboxylic acid instead of a sulfonic acid in the binding motif demonstrate that the sulfonic acid has superior binding strength.

    14. Spontaneous polymerization mechanism of electron-accepting substituted quinodimethane with vinyl ether and cyclic ketene acetal (pages 3800–3811)

      Yukihiro Mitsuda, Takashige Fujikawa, Katsumi Nakasaka, Takahiro Uno, Masataka Kubo and Takahito Itoh

      Article first published online: 23 JUN 2004 | DOI: 10.1002/pola.20235

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      Spontaneous reactions of an electron-accepting substituted quinodimethane (QM-1) with butyl vinyl ether (BVE) and 2-methylene-1,3-dioxepane (MDOP) were investigated. The spontaneous polymerization was proposed to proceed via a zwitterionic intermediate taking two forms, gauche and trans, depending on the bulkiness of the comonomers.

    15. Solid-phase incorporation of gaseous carbon dioxide into oxirane-containing copolymers (pages 3812–3817)

      Bungo Ochiai, Tokinori Iwamoto, Toyoharu Miyagawa, Daisuke Nagai and Takeshi Endo

      Article first published online: 28 JUN 2004 | DOI: 10.1002/pola.20234

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      Carbon dioxide was incorporated into poly(glycidyl methacrylate-co-methyl methacrylate) by a solid-phase reaction, which transformed the pendent oxirane moieties into cyclic carbonate moieties, with quaternary ammonium halide catalysts. The incorporation of carbon dioxide into the copolymer led to soluble carbonate-containing polymers, whereas the incorporation of carbon dioxide into the glycidyl methacrylate homopolymer produced an insoluble product. The copolymer composition, reaction temperature, and catalyst amount affected the incorporation efficiency and the side reaction that caused crosslinking.

    16. Antimicrobial polymers containing melamine derivatives. I. Preparation and characterization of chloromelamine-based cellulose (pages 3818–3827)

      Martha Braun and Yuyu Sun

      Article first published online: 23 JUN 2004 | DOI: 10.1002/pola.20270

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      2-Amino-4-chloro-6-hydroxy-s-triazine (ACHT) was synthesized by the controlled hydrolysis of 2-amino-4,6-dichloro-s-triazine. ACHT was grafted onto cotton cellulose at room temperature by a cold-pad-batch treatment process. Upon chlorination reactions, the amino group of covalently bound ACHT was transformed into N-halamine structure, providing potent, durable, and rechargeable antimicrobial actvities against both gram-negative and gram-positive bacteria.

    17. Radical copolymerization of maleimide with ethyl α-ethylacrylate and α-ethylacrylic acid via RAFT (pages 3828–3835)

      Yong Ren, Zhongliang Zhu and Junlian Huang

      Article first published online: 23 JUN 2004 | DOI: 10.1002/pola.20199

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      The copolymerization of maleimide (MI) with α-ethylacrylic acid (EAA) and with ethyl α-ethylacrylate (EEA) in the presence of 2-phenylprop-2-yl dithiobenzoate (PPDB) was investigated. The copolymerization of MI and EAA was difficult to conduct with the reversible addition–fragmentation chain transfer (RAFT) mechanism. When the carboxylic group of EAA was esterified, then copolymerization went well via RAFT, and alternating copolymers with controlled molecular weight were obtained. Combining by electron spin resonance showed a different result. It was found that before 30% of the comonomer conversion had occurred, the copolymer of poly(EEA-co-MI) showed increasing molecular weight of increasing with the conversion and a rather narrow molecular weight distribution; then the molecular weight of the copolymer began to retard. This phenomenon of retardation was aggravated at high temperature.

    18. Cobaltic accelerator for the methylene blue photoinitiation system in aqueous acrylate solution (pages 3836–3841)

      Jianwen Yang and Douglas C. Neckers

      Article first published online: 23 JUN 2004 | DOI: 10.1002/pola.20213

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      A near-infrared spectrometer was used to follow the photopolymerization of aqueous multifunctional acrylate. Methylene blue (MB) and triethanolamine were used as the basic photoinitiation system, and novel accelerators to the two-component initiation system were investigated. The three-component photoinitiation systems containing cobaltic complexes as accelerators were found to be very efficient in initiating the polymerization of the aforementioned water-soluble monomer, and the efficiency was higher than that initiated by MB/triethanolamine/diphenyl iodonium chloride. Twin redox cycles between MB and cobaltic complexes was proposed to explain the acceleration effect of the cobaltic complexes.

    19. Surface grafting onto SiC nanoparticles with glycidyl methacrylate in emulsion (pages 3842–3852)

      Ying Luo, Min Zhi Rong, Ming Qiu Zhang and Klaus Friedrich

      Article first published online: 23 JUN 2004 | DOI: 10.1002/pola.20227

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      Chemically grafting of polyglycidyl methacrylate onto the surface of nano-SiC particles can be accomplished through surfactant-free emulsion polymerization. It is found that the pretreatment of nano-SiC with A silane coupling agent is a key factor enabling the grafting reaction. The emulsion polymerization loci are proven to be located at the surface of the pretreated SiC nanoparticles due to the great number of the nanoparticles and their hydrophobic surface feature. This mechanism is particularly important to ensure the effective encapsulating and grafting of polyglycidyl methacrylate surrounding the nanoparticles.

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    1. Effect of dendritic architecture on localized free volume of poly(ether ketone)s as probed by positron annihilation spectroscopy (pages 3853–3859)

      Seung-Yeop Kwak, Chunqing He, Takenori Suzuki and Sang-Hoon Lee

      Article first published online: 23 JUN 2004 | DOI: 10.1002/pola.20222

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      Model poly(ether ketone)s (PEKs) with architectural variations were studied by positron annihilation lifetime spectroscopy (PALS) to estimate the average void sizes on a sub-nanometer scale, in conjunction with the hyperbranched (H-), the linear (L-), and their 50:50 block combination (HLH-) structures. The PALS distribution confirmed the unique molecular architecture of the hyperbranched polymer, consisting of an interior cavity space formed by loosely linked core and chain ends of relatively tighter free volume space.

    2. Nonhemolytic abiogenic polymers as antimicrobial peptide mimics (pages 3860–3864)

      Lachelle Arnt, Klaus Nüsslein and Gregory N. Tew

      Article first published online: 23 JUN 2004 | DOI: 10.1002/pola.20304

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      Cationic, facially amphiphilic poly(m-phenylene ethynylene)s were used to investigate whether or not simple polymers can mimic the essential biological activity of host defense peptides. The minimal inhibitory concentrations for two bacteria, Escherichia coli and Bacillus subtilis, were determined and used as models for gram-negative and gram-positive bacteria. Hemolytic activity showed that selectivity toward bacterial cells can occur by the control of the hydrophobic balance and the molecular weight of the system.

    3. Synthesis of gel-type polymer beads from ionic liquid monomers (pages 3865–3869)

      Mark J. Muldoon and Charles M. Gordon

      Article first published online: 25 JUN 2004 | DOI: 10.1002/pola.20299

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      The synthesis of polymer beads made entirely from ionic liquid monomers is reported for the first time in this preliminary study. Gel-type beads were prepared by the suspension polymerization of imidazolium-based ionic liquid monomers. This simple preparation resulted in polymer beads with potential applications in catalysis, separation technology, and ion-exchange resins.

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    1. Synthesis and phase behavior of side-chain liquid-crystalline polymers containing malachite green lactone groups (pages 3870–3878)

      Jian-She Hu, Bao-Yan Zhang, Ying Wang and Fan-Bao Meng

      Article first published online: 25 JUN 2004 | DOI: 10.1002/pola.20266

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      Thermochromic liquid-crystalline polymers were synthesized and characterized. The mesogenic properties and phase behavior were investigated with differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy, and X-ray diffraction measurements. The effect of the concentration of dye side groups on the phase behavior of the polymers was examined. Those polymers containing less than 20 mol % dye groups had good solubility, reversible phase transitions, wider mesophase temperature ranges, and higher thermal stability.

    2. Photocrosslinkable smart terpolymers responding to pH, temperature, and ionic strength (pages 3879–3886)

      Krzysztof Szczubiałka, Łukasz Moczek, Sebastian Błaszkiewicz and Maria Nowakowska

      Article first published online: 25 JUN 2004 | DOI: 10.1002/pola.20249

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      A series of stimuli-responsive terpolymers of acrylic acid, N-isopropylacrylamide, and cinnamoyloxyethyl acrylate were synthesized and studied with UV absorption and fluorescence spectroscopy. The polymers were photocrosslinkable when irradiated with UV light. Moreover, they responded to temperature, pH, and ionic strength. The lower critical solution temperature of the polymers could be adjusted through changes in the monomer composition, pH, and ionic strength. The response of the polymers to stimuli was studied with fluorescence probes.

    3. Preparation of novel macromonomers and study of their polymerization (pages 3887–3896)

      Guohua Deng and Yongming Chen

      Article first published online: 25 JUN 2004 | DOI: 10.1002/pola.20241

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      Novel macromonomers of polystyrene and poly(tert-butyl acrylate) containing a methacryloyl group as a polymerizable unit and two chains of the same length were prepared through the combination of atom transfer radical polymerization (ATRP) and posttransformation of the hydroxyl group into a methacryloyl group. The homopolymerization and copolymerization of the novel macromonomers were investigated.

    4. Synthesis and characterization of crosslinked chitosan formed by γ irradiation in the presence of carbontetrachloride as a sensitizer (pages 3897–3909)

      S. P. Ramnani, C. V. Chaudhari, N. D. Patil and S. Sabharwal

      Article first published online: 25 JUN 2004 | DOI: 10.1002/pola.20230

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      Synthesis of crosslinked chitosan using γ irradiation in the presence of carbon tetrachloride as a sensitizer is carried out. The resultant crosslinked product (yellow in color) is characterized by elemental analysis, which shows the presence of chlorine. The crosslinked chitosan on hydrolysis with alkali results in the formation of another product that retains the crosslinked structure but does not have chlorine in it. Gel formatting characteristics of both these products have been studied. The crosslinked chitosan and its hydrolysis product are further characterized by various physical methods such as X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FTIR), and thermogravimetry. Based on the results, a probable mechanism of crosslinking whereby chitosan chains are crosslinked by a >CCL2 group is suggested.

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