Macromolecular Rapid Communications

Cover image for Vol. 30 Issue 23

Special Issue: Acrylate Free Radical Polymerization: From Mechanism to Polymer Design

December 1, 2009

Volume 30, Issue 23

Pages 1955–2055

Issue edited by: C. Barner-Kowollik

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Contents
    4. Editorial
    5. Essay
    6. Communications
    1. Macromol. Rapid Commun. 23/2009

      Nasir M. Ahmad, Bernadette Charleux, Céline Farcet, Christopher J. Ferguson, Scott G. Gaynor, Brian S. Hawkett, Frank Heatley, Bert Klumperman, Dominik Konkolewicz, Peter A. Lovell, Krzysztof Matyjaszewski and Rajan Venkatesh

      Version of Record online: 1 DEC 2009 | DOI: 10.1002/marc.200990060

      Thumbnail image of graphical abstract

      Cover: Branching in poly(n-butyl acrylate) arises from chain transfer to polymer, which is shown to proceed to lower extents in controlled radical polymerizations than in conventional free-radical polymerization and explained in terms of differences in highly reactive short-chain radical concentration. Further details can be found in the article by N. M. Ahmad, B. Charleux, C. Farcet, C. J. Ferguson, S. G. Gaynor, B. S. Hawkett, F. Heatley, B. Klumperman, D. Konkolewicz, P. A. Lovell,* K. Matyjaszewski, and R. Venkatesh on page 2002.

  2. Contents

    1. Top of page
    2. Cover Picture
    3. Contents
    4. Editorial
    5. Essay
    6. Communications
  3. Editorial

    1. Top of page
    2. Cover Picture
    3. Contents
    4. Editorial
    5. Essay
    6. Communications
    1. Acrylate Free Radical Polymerization: From Mechanism to Polymer Design (pages 1961–1963)

      Christopher Barner-Kowollik

      Version of Record online: 16 OCT 2009 | DOI: 10.1002/marc.200900676

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      The free radical polymerization of acrylates is a fascinating area: The underpinning reaction mechanism is highly complex and only recently a coherent picture as well as reliable rate coefficients are starting to emerge. In addition, functional acrylates are important building blocks for complex macromolecular designs for a wide range of applications. The current special issue will collate the latest advances in the field – from mechanism to polymer design.

  4. Essay

    1. Top of page
    2. Cover Picture
    3. Contents
    4. Editorial
    5. Essay
    6. Communications
    1. Historic Account of the Development in the Understanding of the Propagation Kinetics of Acrylate Radical Polymerizations (pages 1964–1968)

      Alex M. van Herk

      Version of Record online: 10 NOV 2009 | DOI: 10.1002/marc.200900574

      Thumbnail image of graphical abstract

      The propagation rate coefficients of the family of acrylate monomers have been a topic of intense scientific studies over the last 10 years or so. In the last decade an almost full understanding of the complicated aspects of acrylate radical polymerizations has been established. In this essay a short historic account of the development in the understanding of acrylate radical polymerizations is given.

  5. Communications

    1. Top of page
    2. Cover Picture
    3. Contents
    4. Editorial
    5. Essay
    6. Communications
    1. EPR Analysis of n-Butyl Acrylate Radical Polymerization (pages 1969–1974)

      Johannes Barth, Michael Buback, Pascal Hesse and Tatiana Sergeeva

      Version of Record online: 12 NOV 2009 | DOI: 10.1002/marc.200900531

      Thumbnail image of graphical abstract

      Temperature dependence of mid-chain radical (MCR) mole fraction, xMCR, during polymerization of butyl acrylate (black symbols). The fractions were obtained by analyzing EPR spectra using two different approaches. One assumes a 3-line MCR conformation in addition to the MCR 7-line in the BA EPR spectrum (filled black squares). The contribution of the 3-line conformation to the MCR part of the EPR signal strongly decreases with temperature (filled blue squares).

    2. Time-Resolved Electron Spin Resonance Spectroscopy of Radicals Formed During Free Radical Polymerizations of Alkyl Acrylates (pages 1975–1980)

      Atsushi Kajiwara

      Version of Record online: 10 NOV 2009 | DOI: 10.1002/marc.200900606

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      Primary propagating radicals obtained by the addition of a diphenylphosphinoyl radical to acrylates have been directly observed using time-resolved electron spin resonance (TR ESR) spectroscopy. The addition rate constants (k2) of the diphenylphosphinoyl radical to the acrylates (initiation rate constants) have been determined. Both steady state ESR and TR ESR provides information on the initiation and propagation kinetics in the radical polymerization of acrylates.

    3. Effect of Intramolecular Transfer to Polymer on Stationary Free Radical Polymerization of Alkyl Acrylates, 4 - Consideration of Penultimate Effect (pages 1981–1988)

      Anatoly N. Nikitin and Robin A. Hutchinson

      Version of Record online: 10 NOV 2009 | DOI: 10.1002/marc.200900419

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      A penultimate model of acrylate polymerization has been proposed to account for reduced reactivity of radicals formed by monomer addition to midchain radicals. Depending on radical reactivity ratio and monomer concentrations, the predictions from this penultimate model for the rate of polymerization, branched level (BL in Figure) and number-degree of polymerization significantly deviate from those of the terminal model.

    4. Surface-Initiated PLP-SEC of Butyl Acrylate and Styrene from Silica Nanoparticles (pages 1989–1994)

      Robert Rotzoll and Philipp Vana

      Version of Record online: 3 NOV 2009 | DOI: 10.1002/marc.200900561

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      For the first time the PLP-SEC technique, which is nowadays the method of choice for determining the propagation rate coefficient, kp, for free-radical polymerization, has been applied to the surface-initiated polymerizations of butyl acrylate and styrene from silica nanoparticles by using an immobilized photoinitiator. Preliminary results show deviations from corresponding kp values obtained in solution, which give reasons for further investigations in the future.

    5. Transfer to Polymer and Long-Chain Branching in PLP–SEC of Acrylates (pages 1995–2001)

      Patrice Castignolles

      Version of Record online: 18 NOV 2009 | DOI: 10.1002/marc.200900530

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      The influence of the long-chain branching on the accuracy of PLP–SEC of acrylates is investigated using multiple-detection size-exclusion chromatography (SEC). The error in determining molecular weight distributions of poly(2-ethylhexyl acrylate) is large due to long-chain branching. As a result, the variations of propagation rate coefficient with alkyl groups in alkyl acrylates or variations with the solvent nature and concentration may be affected.

    6. Chain Transfer to Polymer and Branching in Controlled Radical Polymerizations of n-Butyl Acrylate (pages 2002–2021)

      Nasir M. Ahmad, Bernadette Charleux, Céline Farcet, Christopher J. Ferguson, Scott G. Gaynor, Brian S. Hawkett, Frank Heatley, Bert Klumperman, Dominik Konkolewicz, Peter A. Lovell, Krzysztof Matyjaszewski and Rajan Venkatesh

      Version of Record online: 24 SEP 2009 | DOI: 10.1002/marc.200900450

      Thumbnail image of graphical abstract

      Branching in poly(n-butyl acrylate) arises from chain transfer to polymer, which is shown to proceed to lower extents in controlled radical polymerizations than in conventional free-radical polymerization. Several rationales are discussed, leading to the conclusion that differences in the concentration of highly reactive short-chain radicals are responsible for the observations.

    7. Consideration of Macromonomer Reactions in n-Butyl Acrylate Free Radical Polymerization (pages 2022–2027)

      Wei Wang, Anatoly N. Nikitin and Robin A. Hutchinson

      Version of Record online: 9 OCT 2009 | DOI: 10.1002/marc.200900445

      Thumbnail image of graphical abstract

      The importance of butyl acrylate macromonomer propagation under conditions of industrial interest is illustrated by experiment and simulation, with the macromonomer reaction responsible for the significant increase in polymer weight-average molecular weight with time. The reactivity of terminally unsaturated chains needs to be considered whenever their production rate (via β-scission) is significant.

    8. Synthesis of a Macromonomer Library from High-Temperature Acrylate Polymerization (pages 2028–2035)

      Anna-Marie Zorn, Thomas Junkers and Christopher Barner-Kowollik

      Version of Record online: 3 NOV 2009 | DOI: 10.1002/marc.200900536

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      A library of acrylate based macromonomers is synthesized via a facile high temperature one pot – on step procedure. The purity of the obtained macromonomers is assessed via electrospray ionization mass spectrometry (ESI-MS) and shown to be close to 90% in all cases.

    9. Synthesis of Cationic Polyelectrolytes by Inverse Microemulsion Polymerization (pages 2036–2041)

      Gemma González, Jesus M. Ugalde, José C. de la Cal and José M. Asua

      Version of Record online: 18 NOV 2009 | DOI: 10.1002/marc.200900528

      Thumbnail image of graphical abstract

      The type of reactor determines the polymer microstructure and hence the application properties of branched cationic flocculants synthesized by inverse microemulsion polymerization. Batch reactors yield polymers with higher molecular weight and more branches than semicontinuous and stirred tank continuous reactors.

    10. Nitroxide-Mediated Copolymerization of 2-Hydroxyethyl Acrylate and 2-Hydroxypropyl Acrylate: Copolymerization Kinetics and Thermoresponsive Properties (pages 2042–2048)

      Richard Hoogenboom, Dragos Popescu, Wiktor Steinhauer, Helmut Keul and Martin Möller

      Version of Record online: 3 NOV 2009 | DOI: 10.1002/marc.200900507

      Thumbnail image of graphical abstract

      Well-defined statistical copolymers of 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate were investigated since these materials are potential candidates for biomedical applications. The copolymerization kinetics are discussed in detail as well as the effect of both polymer composition and polymer concentration on the cloud points.

    11. Star-Shaped Polyacrylates: Highly Functionalized Architectures via CuAAC Click Conjugation (pages 2049–2055)

      Mieke Lammens, David Fournier, Martin W. M. Fijten, Richard Hoogenboom and Filip Du Prez

      Version of Record online: 7 OCT 2009 | DOI: 10.1002/marc.200900494

      Thumbnail image of graphical abstract

      Well-defined end-functionalized poly(isobornyl acrylate) (PiBA) star-shaped polymers with up to 29 arms are successfully synthesized by a combination of ATRP and azide–alkyne click chemistry. A variety of functional molecules and polymers are introduced onto the shell of the PiBA star-shaped polymers.

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