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Synthesis of isotactic poly[α-(hydroxymethyl)acrylate] by anionic polymerization of the protected monomer

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Abstract

Isotactic poly[methyl α-(hydroxymethyl)acrylate] was prepared via anionic polymerization of the respective monomer protected with trimethylsilyl group (1-TMS) initiated with isopropyl α-lithioisobutyrate (Li-iPrIB) in toluene at −78 °C. The polymerization proceeded in high isotactic specificity similarly to the case of α-(alkoxymethyl)acrylate, although the monomer conversion was low (~18 %) due to the self-terminating reaction accompanying the elimination of trimethylsilanolate anion. The monomer conversion could be improved to ca. 75 % in the polymerizations with an excess amount of LiOSiMe3, which would interact with and stabilize the propagating species to suppress the self-terminating reaction. This was a sharp contrast to the polymerization of α-(methoxymethoxymethyl)acrylate (1-MOM), an acetal protected monomer, where the addition of LiOSiMe3 enhanced the self-termination. Consequently, the structure of protective group affects the polymerization behavior. For the resulting poly(1-TMS), the deprotection by acid hydrolysis quantitatively afforded isotactic poly[methyl α-(hydroxymethyl)acrylate].

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Acknowledgments

The authors would like to thank Nippon Shokubai Co. Ltd. for the kind gift of methyl α -(hydroxymethyl)acrylate. This work was supported by JSPS KAKENHI Grant Number 26810069.

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Authors and Affiliations

  1. Faculty of Textile Science and Technology, Shinshu University, 3-15-1 Tokida, Ueda, Nagano, 386-8567, Japan

    Yasuhiro Kohsaka

  2. Department of Chemistry, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka, 560-8531, Japan

    Kazuki Yamamoto, Kazuha Suzawa & Tatsuki Kitayama

Authors
  1. Yasuhiro Kohsaka
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  2. Kazuki Yamamoto
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  3. Kazuha Suzawa
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  4. Tatsuki Kitayama
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Correspondence to Yasuhiro Kohsaka.

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Kohsaka, Y., Yamamoto, K., Suzawa, K. et al. Synthesis of isotactic poly[α-(hydroxymethyl)acrylate] by anionic polymerization of the protected monomer. Polym. Bull. 74, 1935–1948 (2017). https://doi.org/10.1007/s00289-016-1813-1

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  • DOI: https://doi.org/10.1007/s00289-016-1813-1

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