Journal of Polymer Science Part A: Polymer Chemistry

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

15 July 2003

Volume 41, Issue 14

Pages 2133–2295

  1. Articles

    1. Top of page
    2. Articles
    1. Poly[1-(trimethylgermyl)-1-propyne] and poly[1-(trimethylsilyl)-1-propyne] with various geometries: Their synthesis and properties (pages 2133–2155)

      V. S. Khotimsky, M. V. Tchirkova, E. G. Litvinova, A. I. Rebrov and G. N. Bondarenko

      Version of Record online: 28 MAY 2003 | DOI: 10.1002/pola.10757

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      Poly[1-(trimethylgermyl)-1-propyne)] and poly[1-(trimethylsilyl)-1-propyne)] with different cis/trans ratios were obtained. The properties of the polymers were defined by their supramolecular ordering, which depended on the lengths of continuous sequences composed of units of analogous microstructures and on the flexibility of macrochains.

    2. Living/controlled radical copolymerization of N-substituted maleimides with styrene in 1-butyl-3-methylimidazolium hexafluorophosphate and anisole (pages 2156–2165)

      You-Liang Zhao, Chuan-Fu Chen and Fu Xi

      Version of Record online: 28 MAY 2003 | DOI: 10.1002/pola.10765

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      The atom transfer radical copolymerization of styrene with N-phenylmaleimide (PhMI), N-cyclohexylmaleimide (ChMI), and N-butylmaleimide (NBMI) initiated with dendritic polyarylether 2-bromoisobutyrates was successfully performed in an ionic liquid (IL), 1-butyl-3-methylimidazolium hexafluorophosphate, and anisole, respectively. The copolymers obtained in IL were of a well-defined molecular weight and low polydispersity (1.05 < Mw/Mn < 1.32) and could be used as a macroinitiator for chain-extension polymerization, suggesting the living nature of the reaction system. The ILs could be recycled in the atom transfer radical polymerization systems without further treatment. The polymerization of various comonomer pairs in IL showed a stronger tendency for alternation than in anisole, and the tendency for alternation decreased in the order PhMI > NBMI > ChMI in ionic liquid and PhMI > ChMI > NBMI in anisole.

    3. Novel ion-exchange resin beads with acid–base indicator property (pages 2166–2170)

      D. Ratna, V. Dalvi, B. C. Chakraborty and P. C. Deb

      Version of Record online: 28 MAY 2003 | DOI: 10.1002/pola.10735

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      A novel ion-exchange resin based on the copolymer of styrene and methyl acrylate was developed in the form of spherical beads, which exhibits an acid–base indicator property. The developed resin exhibited better performance in demineralization of water as compared with polystyrene-based ion-exchange resin.

    4. Shape and diffusion of the monomer-controlled copolymerization of ethylene and α-olefins over Cp2ZrCl2 confined in the nanospace of the supercage of NaY (pages 2171–2179)

      Young Soo Ko and Seong Ihl Woo

      Version of Record online: 28 MAY 2003 | DOI: 10.1002/pola.10762

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      Cp2ZrCl2 confined inside the supercage of NaY zeolites [NaY/methylaluminoxane (MAO)/Cp2ZrCl2] exhibited the shape and diffusion of a monomer-controlled copolymerization mechanism that strongly depended on the molecular structure of the monomer and its size. Ethylene–propylene, ethylene/1-hexene, ethylene.1-octene, and ethylene–isobutene copolymerizations were performed, and the results showed evidence of the shape and diffusion of a monomer-controlled mechanism. The content of the comonomer in the copolymer chain prepared with NaY/MAO/Cp2ZrCl2 decreased by about one-half in comparison with that of Cp2ZrCl2. The copolymers of NaY/MAO/Cp2ZrCl2 had narrow comonomer distributions, whereas those of homogeneous Cp2ZrCl2 were broad.

    5. Chain composition dependence of luminescence properties for copolymers of 2-methoxy-5-2′-ethyl-hexyloxy-1,4-phenylenevinylene and 2,3-diphenyl-5-octyl-1,4-phenylenevinylene (pages 2180–2186)

      Chi-Chia Chiu, King-Fu Lin and Hsuan-Liang Chou

      Version of Record online: 28 MAY 2003 | DOI: 10.1002/pola.10766

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      The copolymerization of 2-methoxy-5-2′-ethyl-hexyloxy-1,4-phenylenevinylene (MEH-PV) and 2,3-diphenyl-5-octyl-1,4-phenylenevinylene via the Gilch route tended to form an alternative copolymer. The MEH-PV units in the copolymer were able to attract the like units from the adjacent chains during the film formation, and this greatly affected the ultraviolet–visible absorption and photoluminescence spectra.

    6. In situ ethylene homopolymerization and copolymerization catalyzed by zirconocene catalysts entrapped inside functionalized montmorillonite (pages 2187–2196)

      Chengbin Liu, Tao Tang, Dun Wang and Baotong Huang

      Version of Record online: 29 MAY 2003 | DOI: 10.1002/pola.10764

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      Ethylene homopolymerizations and copolymerizations were catalyzed by zirconocene catalysts entrapped inside functionalized montmorillonites that had been rendered organophilic via the ion exchange of the interlamellar cations of layered montmorillonite with hydrochlorides of L-amino acids or their methyl esters, with or without the further addition of hexadecyltrimethylammonium bromide. This was effective for the synthesis of polyethylenes with controlled molecular weights, chemical compositions and structures, and properties, including the bulk density.

    7. Photocrosslinkable liquid-crystalline block copolymers with coumarin units synthesized with atom transfer radical polymerization (pages 2197–2206)

      Yanqing Tian, Xiangxing Kong, Yu Nagase and Tomokazu Iyoda

      Version of Record online: 29 MAY 2003 | DOI: 10.1002/pola.10767

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      This article describes the synthesis, thermal and photochemical properties, and morphologies of a new class of liquid-crystalline homo- and block copolymers with photocrosslinkable coumarin units.

    8. Synthesis and copolymerization of new phosphorus-containing acrylates (pages 2207–2217)

      Duygu Avci and Aylin Ziylan Albayrak

      Version of Record online: 2 JUN 2003 | DOI: 10.1002/pola.10768

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      Two phosphorus-containing acrylate monomers were synthesized from the reaction of ethyl α-chloromethyl acrylate and t-butyl α-bromomethyl acrylate with triethyl phosphite. Additionally, α-(chloromethyl)acryloyl chloride (CMAC) was reacted with diethyl (hydroxymethyl)phosphonate to obtain a new monomer with identical ester and ether moieties. A new derivative of CMAC with mixed ester and ether groups was synthesized by substitution, first with diethyl (hydroxymethyl)phosphonate and then with sodium acetate. The selective hydrolysis of the monomers with trimethylsilyl bromide gave phosphonic acid monomers. The homopolymerization and copolymerization behavior of the monomers and the thermal stabilities of the polymers were investigated.

    9. Intrachain chromophore interactions in silanylene-spaced divinylbenzene copolymers (pages 2218–2231)

      Tsyr-Yuan Hwu, Sourav Basu, Ruey-Min Chen, Yen-Ju Cheng, Jui-Hung Hsu, Wunshain Fann and Tien-Yau Luh

      Version of Record online: 2 JUN 2003 | DOI: 10.1002/pola.10763

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      A range of silanylene-spaced divinylbenzene copolymers (1) and the corresponding monomers (2) have been synthesized by the rhodium-catalyzed hydrosilylation of the corresponding bisalkynes with bissilyl hydrides, and the photophysical properties of 1 and 2 have been investigated. The silicon moiety in 1 serves as an insulating tetrahedral spacer that makes 1 highly folded. The two chromophores may be in close proximity such that a ground-state intrachain interaction between two conjugated moieties through space might occur.

    10. Evolution of multimodal particle size distribution in vinyl acetate/butyl acrylate emulsion copolymerizations (pages 2232–2249)

      Charles D. Immanuel, Timothy J. Crowley, Edward S. Meadows, Cajetan F. Cordeiro and Francis J. Doyle III

      Version of Record online: 5 JUN 2003 | DOI: 10.1002/pola.10760

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      This article presents a study on the engineering of multimodal distributions in semibatch emulsion polymerizations with nonionic surfactants. Various methods of producing multimodal distributions are demonstrated, and the sensitivity of the process to the properties of the reagents are analyzed. A test-bed emulsion polymerization system, equipped with instrumentation to measure particle size distribution (capillary hydrodynamic fractionator) and monomer conversion (densitometer and flow meters), is used for this purpose. The process is monitored and controlled with an industrial distributed control system, which enables the automated operation of the process through sequential or logic controllers operating over lower level proportional integral derivative controllers.

    11. Preparation and properties of high molecular weight polyethoxysiloxanes stable to self-condensation by acid-catalyzed hydrolytic polycondensation of tetraethoxysilane (pages 2250–2255)

      Yoshimoto Abe, Ryosuke Shimano, Koji Arimitsu and Takahiro Gunji

      Version of Record online: 6 JUN 2003 | DOI: 10.1002/pola.10739

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      The acid-catalyzed controlled hydrolytic polycondensation of tetraethoxysilane (TEOS) provided polyethoxysiloxanes with weight-average molecular weights of 2300–11,700, which depended on the reaction molar ratios of the water, catalyst, and solvent to TEOS. They were soluble in common organic solvents and stable to self-condensation and were characterized with high silica contents of up to 67%.

    12. Complexation of copper(II) ions with imidazole–carboxylic polymeric systems (pages 2256–2263)

      V. V. Annenkov, E. N. Danilovtseva, V. V. Saraev and A. I. Mikhaleva

      Version of Record online: 6 JUN 2003 | DOI: 10.1002/pola.10769

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      The interaction of poly(1-vinylimidazole-co-acrylic acid) and interpolymer complex poly(acrylic acid)/poly(1-vinylimidazole) with copper(II) ions in aqueous medium was accompanied by synergism between coordination with metal ions and intramolecular hydrogen or ionic bonds. The interpolymer complex was an effective system for binding, extracting, and concentrating copper ions from water.

    13. Influence of the bisphenol structure on the direct synthesis of sulfonated poly(arylene ether) copolymers. I (pages 2264–2276)

      William L. Harrison, Feng Wang, Jeffery B. Mecham, Vinayak A. Bhanu, Melinda Hill, Yu Seung Kim and James E. McGrath

      Version of Record online: 5 JUN 2003 | DOI: 10.1002/pola.10755

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      Proton exchange membranes based on direct nucleophilic step copolymerization of disulfonated and control activated aromatic halides with four bisphenols are discussed. In particular, the comparison of bisphenol A, biphenol, hydroquinone, and bisphenol A–F represented by the corresponding structures are reported.

    14. A series of new high-performance materials based on poly[4′-fluorophenyl-bis(4-phenyl)phosphine oxide] (pages 2277–2287)

      Laura A. Rusch-Salazar and Valerie V. Sheares

      Version of Record online: 5 JUN 2003 | DOI: 10.1002/pola.10745

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      A new series of high-performance poly(arylene phosphine oxide) materials were synthesized postpolymerization from fluorinated poly(arylene phosphine oxide) (f-PAPO). The new materials had increased solubility and film-forming ability over the parent f-PAPO. With the careful choice of the nucleophile, the thermal stability was also increased. f-PAPO was synthesized via Ni(0) coupling from an aromatic chloride monomer, and this resulted in a material with an intrinsic viscosity of 0.235 dL/g, a glass transition of 320 °C, and a char yield of 54% at 650 °C in air. Copolymers were synthesized with 2,5-dichloro-4′-fluorobenzophenone to improve the solubility of f-PAPO without the loss of thermal stability and to be used as an epoxy cure agent after substitution.

    15. Nonstoichiometric polyelectrolyte complex of carboxymethylcellulose and N-methylated poly(2-vinylpyridine): Formation of a gel-like structure (pages 2288–2295)

      B. Vishalakshi and Soumyadeb Ghosh

      Version of Record online: 6 JUN 2003 | DOI: 10.1002/pola.10771

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      Polyelectrolyte complexes between carboxymethylcellulose and N-methylated poly(2-vinylpyridine), at a nonstoichiometric mixing ratio, were studied with viscometry, turbidimetry, electrophoresis, and optical spectroscopy. A gel-like structure was proposed for the nonstoichiometric polyelectrolyte complexes. Two steps of complex formation—ionic bond formation followed by its rearrangement—were identified. The conformational change of the polyelectrolyte chains in the complex, responsible for the slower and latter step, was followed by viscometry, and the results were interpreted on the basis of a model proposed for the kinetics of swelling of hydrogels.

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