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Synthesis of Block Copolymers of Styrene with D,L-Lactide by the Sequential Controlled Cationic Polymerization and Ring-Opening Anionic Polymerization

  • Polymerization
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Abstract

The cationic polymerization of styrene initiated by the system 2-chloro-2-phenylpropane–TiCl4–pyridine is studied in a mixture CH2Cl2–n-hexane at a temperature of –80°С. It is shown that under these conditions polymerization occurs via the living mechanism at [monomer]: [initiator] ≤ 100. The method of preparing polystyrenes with terminal primary hydroxyl groups (Mn = 4000–10000 g/mol) by the sequential controlled cationic polymerization of styrene and the in situ alkylation of 4-phenoxy-1-butanol by polystyrene macrocations is proposed. The resulting functionalized polystyrenes are used as macroinitiators of anionic-coordination ring-opening polymerization of D,L-lactide in the presence of tin bis(2-ethyl hexanoate) [Sn(Oct)2] in toluene at 80°С. Copolymers polystyrene-block-poly(D,L-lactide) with the controlled length of the poly(D,L-lactide) block (Mn = 10000–17000 g/mol) and a relatively low molecular-weight distribution (Mw/Mn = 1.6–1.8) are synthesized. Formation of the block copolymers is confirmed by 1Н NMR spectroscopy, gel-permeation chromatography, and atomic force microscopy.

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Authors and Affiliations

  1. Research Institute for Physical Chemical Problems of the Belarusian State University, Minsk, 220006, Belarus

    P. A. Nikishev, Yu. A. Piskun, I. V. Vasilenko, L. V. Gaponik & S. V. Kostjuk

  2. Faculty of Chemistry, Belarusian State University, Minsk, 220006, Belarus

    P. A. Nikishev

  3. Institute of Photon Technologies, Crystallography and Photonics Scientific Center, Russian Academy of Sciences, Troistk, Moscow, 142190, Russia

    P. S. Timashev & A. A. Akovantseva

  4. Institute for Regenerative Medicine, Sechenov First Moscow State Medical University, Moscow, 119991, Russia

    P. S. Timashev

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  1. P. A. Nikishev
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  2. Yu. A. Piskun
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  3. I. V. Vasilenko
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Correspondence to P. A. Nikishev.

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Original Russian Text © P.A. Nikishev, Yu.A. Piskun, I.V. Vasilenko, L.V. Gaponik, P.S. Timashev, A.A. Akovantseva, S.V. Kostjuk, 2017, published in Vysokomolekulyarnye Soedineniya, Seriya B, 2017, Vol. 59, No. 6, pp. 413–423.

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Nikishev, P.A., Piskun, Y.A., Vasilenko, I.V. et al. Synthesis of Block Copolymers of Styrene with D,L-Lactide by the Sequential Controlled Cationic Polymerization and Ring-Opening Anionic Polymerization. Polym. Sci. Ser. B 59, 655–664 (2017). https://doi.org/10.1134/S1560090417060070

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  • DOI: https://doi.org/10.1134/S1560090417060070

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