Journal of Polymer Science Part A: Polymer Chemistry

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

15 March 2002

Volume 40, Issue 6

Pages 731–808

  1. Articles

    1. Top of page
    2. Articles
    1. Synthesis and characterization of water-soluble barbiturate- and thiobarbiturate-functionalized polystyrene (pages 731–737)

      S. Raja and R. Dhamodharan

      Article first published online: 25 JAN 2002 | DOI: 10.1002/pola.10154

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      Polystyrene homopolymer quantitatively functionalized at the para postion with diethyl oxomalonate functionality was subjected to a condensation reaction with urea and thiourea in the presence of sodium methoxide in methanol. Thus, several water-soluble copolymers of styrene with barbiturate- and thiobarbiturate-functionalized styrene were synthesized and characterized. Thiobarbiturate-functionalized polystyrenes were fabricated to remove 450 ppm of Cu(II) ions from 1 L of an aqueous solution of Cu(II) ions.

    2. Poly(3,4-ethylenedioxythiophene)-based copolymers for biosensor applications (pages 738–747)

      Alexander Kros, Roeland J. M. Nolte and Nico A. J. M. Sommerdijk

      Article first published online: 25 JAN 2002 | DOI: 10.1002/pola.10159

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      The synthesis of 3,4-ethylenedioxythiophene (EDOT) derivatives bearing functional groups is described. Various copolymers of EDOT and modified EDOT containing hydroxyl groups were electrochemically prepared. To one of these copolymers, glucose oxidase was covalently coupled. The obtained material could be used as a biosensor in the amperometric detection of glucose under aerobic and anaerobic conditions.

    3. Metalization of polymer beads via polymer-supported hydrazines as reducing agents (pages 748–754)

      Niyazi Bicak, Şana Sungur, Nükhet Tan, Farid Bensebaa and Yves Deslandes

      Article first published online: 25 JAN 2002 | DOI: 10.1002/pola.10158

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      A new method has been developed for zero-valent metal deposition onto solid polymer surfaces. With polymer-supported hydrazine functions as reducing agents, copper, silver, and nickel were deposited onto glycidyl methacrylate-based polymers (≤4.26 mmol g−1) from ammoniacal metal-ion solutions.

    4. Preparation of monolithic polymers with controlled porous properties for microfluidic chip applications using photoinitiated free-radical polymerization (pages 755–769)

      Cong Yu, Mingcheng Xu, Frantisek Svec and Jean M. J. Fréchet

      Article first published online: 31 JAN 2002 | DOI: 10.1002/pola.10155

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      A broad variety of monolithic macroporous polymers with both controlled chemistry and porous properties was prepared within fused silica capillaries and on microfluidic chips using UV-initiated free-radical polymerization in a photolithographic manner. The chemistry of the monoliths with reactive, hydrophilic, hydrophobic, and ionizable functionalities is defined by the composition of the monomer mixture used for the polymerization. Because the UV polymerization is carried out at room temperature, even low molecular weight alcohols and other low boiling point solvents could safely be used. Performance of these monoliths is demonstrated with the separation of derivatized amines by means of capillary electrochromatography in the reversed-phase mode and with a solid-phase microextraction with enrichment of green fluorescent protein from its dilute solution by a factor of 1000.

    5. Effect of the chemical nature and length of spacer arms on the covalent grafting of fluorinated molecular probes at the surface of poly(ethylene terephthalate) membrane (pages 770–781)

      Stéphane Biltresse, Dimitri Descamps, Cathy Henneuse-Boxus and Jacqueline Marchand-Brynaert

      Article first published online: 31 JAN 2002 | DOI: 10.1002/pola.10156

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      A series of fluorinated molecular probes has been synthesized that are characterized by spacer arms of various lengths and polarities. The previous molecules have been covalently fixed on the surface of poly(ethylene terephthalate) (PET) membranes via activated hydroxyl chain endings. X-ray photoelectron microscopic analysis of the grafted samples allowed us to quantify the PET surface reactivity; the results were within 40–50 pmol/cm2 of fixed probes, independent of the length and hydrophilicity of the spacer arms.

    6. Viscosity effects in cobaloxime-mediated catalytic chain-transfer polymerization of methacrylates (pages 782–792)

      G. Evan Roberts, Thomas P. Davis, Johan P. A. Heuts and Gregory T. Russell

      Article first published online: 31 JAN 2002 | DOI: 10.1002/pola.10152

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      The effect of bulk viscosity on the cobaloxime-mediated catalytic chain-transfer polymerization of methacrylates at 60 °C was investigated by both the addition of high molecular weight poly(methyl methacrylate) to methyl methacrylate polymerization and the dilution of benzyl methacrylate polymerization by toluene. Although the results indicate that the bulk viscosity is not directly linked to the chain-transfer activity, the results do not necessarily disprove a diffusion-controlled reaction rate. Considering the published data to date we are not able to distinguish between a diffusion-controlled reaction rate or a mechanism directly affected by the methacrylate substituent.

    7. Modeling of photobleaching for the photoinitiation of thick polymerization systems (pages 793–808)

      G. A. Miller, L. Gou, V. Narayanan and A. B. Scranton

      Article first published online: 1 FEB 2002 | DOI: 10.1002/pola.10162

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      We present a mathematical description of the spatial and temporal evolution of the light intensity gradient, initiator concentration gradient, and initiation rate profiles for photobleaching initiator systems with a model that includes the effects of absorption by the initiator fragments, absorption by the monomer, and diffusion of the initiator. Simulation results have confirmed that the initiation rate profile resembles a wave front that propagates through the sample and that there is an optimum initiator concentration for efficient photopolymerization of thick samples. As either the initiator concentration or molar absorptivity is increased, the initiation rate at the peak of the wave front increases, the breadth of the propagating front decreases, and the rate of spatial propagation through the sample decreases, as illustrated in the figure. In contrast, the maximum photoinitiation rate and rate of spatial propagation of the initiation front can be simultaneously increased with an increasing initiator quantum yield or a decreasing absorptivity of the monomer or photolysis products.

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