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RAFT-mediated emulsion polymerization of vinyl acetate: a challenge towards producing high molecular weight poly(vinyl acetate)

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Abstract

The preparation of poly(vinyl acetate) with well-controlled structure has received a great deal of interest in recent years because of a large number of developments in living radical polymerization techniques. Among these techniques, the use of reversible addition–fragmentation chain transfer (RAFT)-mediated polymerization has been employed for the controlled polymerization of vinyl acetate due to the high susceptibility of this monomer towards chain transfer reactions. Here, a novel water-soluble N,N-dialkyl dithiocarbamate RAFT agent has been prepared and employed in the emulsion polymerization of vinyl acetate. The kinetic results reveal that the polymerization nucleation mechanism changes from homogeneous to micellar and RAFT-generated radicals can change the kinetic behavior from conventional emulsion polymerization to living radical polymerization. At higher concentrations of the modified RAFT agent, as a result of an aqueous phase reaction between RAFT and sulfate radicals, relatively more hydrophobic radicals are generated, which favors entry and propagation into micelles swollen with monomer. This observation was determined from the investigation of the polymerization rate and measurements of the average particle diameter and the number of particles per liter of the aqueous phase. Molecular weight analysis also demonstrated the participation of the RAFT agent in the polymerization in such a way as to restrict chain transfer reactions. This was determined by examining the evolution of polymer chain length and attaining higher molecular weights, even up to 50 % greater than the samples obtained from the conventional emulsion polymerization of vinyl acetate in the absence of the synthesized modified RAFT agent.

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Acknowledgments

ARM wishes to express his gratitude to the Iran Polymer and Petrochemical Institute for providing financial support to participate in this project at Lehigh University. Also, financial support from the Emulsion Polymers Institute's Industrial Liaison Program Lehigh University is gratefully acknowledged.

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Authors and Affiliations

  1. Emulsion Polymers Institute, Lehigh University, 111 Research Drive, Bethlehem, PA, 18015, USA

    Funian Zhao, Eric S. Daniels, Andrew Klein & Mohamed S. El-Aasser

  2. Department of Chemical Engineering, Lehigh University, 111 Research Drive, Bethlehem, PA, 18015, USA

    Funian Zhao, Andrew Klein & Mohamed S. El-Aasser

  3. Polymer Science Department, Iran Polymer and Petrochemical Institute, P. O. Box 14965/115, Tehran, 14967, Iran

    Ali Reza Mahdavian

  4. Faculty of Chemistry, Tarbiat Moallem University, 49 Mofateh St, Tehran, Iran

    Mohammad Bagher Teimouri

Authors
  1. Funian Zhao
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  2. Ali Reza Mahdavian
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  3. Mohammad Bagher Teimouri
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  4. Eric S. Daniels
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  5. Andrew Klein
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  6. Mohamed S. El-Aasser
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Corresponding author

Correspondence to Eric S. Daniels.

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Zhao, F., Mahdavian, A.R., Teimouri, M.B. et al. RAFT-mediated emulsion polymerization of vinyl acetate: a challenge towards producing high molecular weight poly(vinyl acetate). Colloid Polym Sci 290, 1247–1255 (2012). https://doi.org/10.1007/s00396-012-2640-z

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  • DOI: https://doi.org/10.1007/s00396-012-2640-z

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