Journal of Polymer Science Part A: Polymer Chemistry

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

1 February 2003

Volume 41, Issue 3

Pages 365–455

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      RAFTing down under: Tales of missing radicals, fancy architectures, and mysterious holes (pages 365–375)

      Christopher Barner-Kowollik, Thomas P. Davis, Johan P. A. Heuts, Martina H. Stenzel, Philipp Vana and Michael Whittaker

      Version of Record online: 16 DEC 2002 | DOI: 10.1002/pola.10567

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      This highlight describes recent developments in reversible addition–fragmentation transfer (RAFT) polymerization. Succinct coverage of the RAFT mechanism is supplemented by details of synthetic methodologies for making a wide range of architectures ranging from stars to combs, microgels, and blocks. In addition, RAFT reactions in different media such as emulsion and ionic liquids receive attention. Finally, a specific example of novel material design is briefly introduced, whereas polymers prepared via RAFT are adopted for microporous/honeycomb membrane design.

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    1. Cobalt-catalyzed alternating and nonalternating copolymerization of carbon monoxide with aziridine (pages 376–385)

      Jiquan Zhao, Errun Ding, Alan M. Allgeier and Li Jia

      Version of Record online: 13 DEC 2002 | DOI: 10.1002/pola.10583

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      The titled novel copolymerization was catalyzed by CH3COCo(CO)3PPh3 and HCo(CO)3PPh3. The polymerization products were characterized with NMR spectroscopy, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, gel permeation chromatography, differential scanning calorimetry, and thermogravimetric techniques.

    2. Kinetics of surface-initiated atom transfer radical polymerization (pages 386–394)

      Jong-Bum Kim, Wenxi Huang, Matthew D. Miller, Gregory L. Baker and Merlin L. Bruening

      Version of Record online: 13 DEC 2002 | DOI: 10.1002/pola.10568

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      The atom transfer radical polymerization of methyl acrylate from immobilized initiators with a Cu/tris[2-(dimethylamino)ethyl]amine catalyst results in a constant but slow growth rate at low catalyst concentrations and rapid growth followed by early termination at higher catalyst concentrations. The juxtaposition of polymerization and termination rates results in an optimum catalyst concentration for achieving maximum film thickness in a given polymerization time. Simulations and experiments demonstrate the strong effect of termination on film growth.

    3. Hydrophilic and hydrophobic copolymer systems based on acrylic derivatives of pyrrolidone and pyrrolidine (pages 395–407)

      Nieves González, Carlos Elvira and Julio San Román

      Version of Record online: 12 DEC 2002 | DOI: 10.1002/pola.10584

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      This article deals with the synthesis of two hydrophilic monomers derived from ethyl pyrrolidone (EPM) and ethyl pyrrolidine (EPyM), their respective homopolymers and copolymers with methyl methacrylate (MMA). The reactivity ratios of these copolymers were found to be rEPM = 1.11, rMMA = 0.76, indicating a higher reactivity than vinylpyrrolidone (rVP = 0.005, rMMA = 4.7) and rEPyM = 1.31, rMMA = 0.92. Behavior in aqueous media was also studied, being dependent on the copolymer composition. Swelling kinetics showed a water transport mechanism case II and the different states of water in the hydrogel were also determined by DSC.

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      Method of preparing clean poly(4-methylstyrene)-block-polyisobutene by the combination of sequential monomer addition and sequential initiation in the solvent CH3Cl (pages 408–412)

      Yuhong Ma, Guanying Wu and Wantai Yang

      Version of Record online: 12 DEC 2002 | DOI: 10.1002/pola.10591

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      A novel method of synthesizing a clean diblock copolymer via cationic polymerization was developed. First, a poly(4-methylstyrene) macroinitiator was prepared, and then a second comonomer (isobutene) and a coinitiator (AlEt2Cl) were added for the initiation of block copolymerization.

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    1. Performance of the Cr[CH(SiMe3)2]3/SiO2 catalyst for ethylene polymerization compared with the performance of the Phillips catalyst (pages 413–419)

      Haruhiko Ikeda, Takashi Monoi and Yasuaki Sasaki

      Version of Record online: 13 DEC 2002 | DOI: 10.1002/pola.10590

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      A silica-supported chromium complex catalyst {Cr[CH(SiMe3)2]3/SiO2}, compared with the Phillips catalyst (CrO3/SiO2), showed a high activity for the polymerization of ethylene without organoaluminum compounds as cocatalysts or scavengers in slurry-phase polymerization under actual industrial conditions used for Phillips catalyst polymerization. The obtained polyethylene had a relatively broad molecular weight distribution and long-chain branching.

    2. Syntheses and properties of novel fluorinated polyamides based on a bis(ether-carboxylic acid) or a bis(ether amine) extended from bis(4-hydroxyphenyl)phenyl-2,2,2-trifluoroethane (pages 420–431)

      Sheng-Huei Hsiao and Wei-Tsun Chen

      Version of Record online: 17 DEC 2002 | DOI: 10.1002/pola.10585

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      Two series of novel fluorinated aromatic polyamides 5 and 7 were prepared from 1,1-bis[4-(4-carboxyphenoxy)phenyl]-1-phenyl-2,2,2-trifluoroethane with various aromatic diamines or from 1,1-bis[4-(4-aminophenoxy)phenyl]-1-phenyl-2,2,2-trifluoroethane with various aromatic dicarboxylic acids with the phosphorylation polyamidation technique. A basic characterization of the obtained polyamides is described. Almost all the fluorinated polyamides displayed relatively higher glass-transition and decomposition temperatures than the corresponding nonfluorinated analogues.

    3. Using diethylphosphites as thermally latent curing agents for epoxy compounds (pages 432–440)

      Yie-Shun Chiu, Ying-Ling Liu, Wen-Lung Wei and Wen-Yu Chen

      Version of Record online: 17 DEC 2002 | DOI: 10.1002/pola.10578

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      Diethylphosphite (DEP) and its derivative exhibited thermally latent properties for epoxy curing reactions through the formation of phosphonic acid as an active species from a reaction of ethanol elimination, which was observed with 1H NMR and pyrolysis gas chromatography/mass spectrometry measurements. The thermally latent properties and curing reaction kinetics of the curing reaction of DEPs with diglycidyl ether of bisphenol A were studied with differential scanning calorimetry. The cured epoxy resins possessed a phosphorous element coming from the DEP derivatives, exhibiting improved flame retardancy.

    4. Composition distribution of ethylene or propylene–norbornene copolymers obtained with zirconocene catalysts (pages 441–448)

      Naofumi Naga and Yukio Imanishi

      Version of Record online: 17 DEC 2002 | DOI: 10.1002/pola.10589

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      Copolymerization of ethylene or propylene and norbornene was carried out with stereospecific zirconocene catalysts at 40 °C combined with metylisobutylaluminoxane. Temperature-rising elution fractionation with cross-fractionation chromatography of the resulting copolymers revealed a narrow molecular weight distribution but a broad distribution of the copolymer composition.

    5. Novel route to poly(p-phenylene vinylene) polymers (pages 449–455)

      Xufeng Wu, Gaoquan Shi, Liangti Qu, Jiaxin Zhang and Feng'en Chen

      Version of Record online: 17 DEC 2002 | DOI: 10.1002/pola.10598

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      A novel solid–liquid two-phase reaction was discovered, which enabled the polymerization of α,α′-dihalogenated-p-xylene and its derivatives into poly(p-phenylene vinylene)s (PPVs). Soluble PPVs with high molar masses and narrow mass dispersities were produced with this technique.

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