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Living Cationic Polymerization of a Vinyl Ether with a Malonic Ester Function

Polymer Journal volume 19, pages 515521 (1987) | Download Citation

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Abstract

Cationic polymerization of diethyl (2-(vinyloxy)ethyl)malonate [1; CH2=CH-OCH2CH2CH(COOC2H5)2], initiated by the hydrogen iodide/iodine (HI/I2) system in toluene at −40°C, led to living polymers consisting of a poly(vinyl ether) backbone and malonic ester pendants. The polymers possessed a very narrow molecular weight distribution (Mw/Mn≤1.1), and their molecular weight (Mn) increased proportionally to monomer conversion or upon addition of a fresh feed of the monomer to a completely polymerized reaction mixture. Polymers of 1 with a fairly high molecular weight (Mw=6×104) and a broad molecular weight distribution (Mw/Mn>2) were obtained with boron trifluoride etherate as initiator otherwise under the same conditions. Saponification of the malonate polymers, followed by neutralization, yielded the corresponding diacid form (3), which underwent decarboxylation on heating in water to give the monocarboxylic acid form (4).

References

  1. 1.

    and , Makromol. Chem., Macromol. Symp., 3, 83 (1986).

  2. 2.

    , , and , Makromol. Chem., Macromol. Symp., 3, 99 (1986).

  3. 3.

    , , and , Macromolecules, 17, 265 (1984).

  4. 4.

    , , and , Macromolecules, 17, 2228 (1984).

  5. 5.

    , , and , J. Am. Chem. Soc., 47, 3083 (1925).

  6. 6.

    , , and , Bull. Soc. Chim. Fr., 267 (1962).

  7. 7.

    , , and , Polym. Prepr., Jpn., 35, 1324 (1986).

  8. 8.

    , , and , Macromolecules, 20, 1 (1987).

  9. 9.

    , , , , and , Macromolecules, 18, 2097 (1985).

  10. 10.

    , , and , J. Org. Chem., 13, 223 (1948).

  11. 11.

    , , and , Polym. Bull., 17, 107 (1987).

  12. 12.

    , , and , Polym. Bull., 14, 515 (1985).

  13. 13.

    See, for example, , , , and , “Organic Chemistry,” 4th ed, McGraw-Hill, New York, N.Y., 1980, p 423.

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  1. Department of Polymer Chemistry, Faculty of Engineering, Kyoto University

    • Toshinobu Higashimura
    • , Takashi Enoki
    •  & Mitsuo Sawamoto

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DOI

https://doi.org/10.1295/polymj.19.515