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Precise Synthesis of Poly(N,N-Dimethylacrylamide) by Group Transfer Polymerization Using a Strong Brønsted Acid and an Amino Silyl Enolate

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Book cover Design and Precise Synthesis of Thermoresponsive Polyacrylamides

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Abstract

This chapter describes the group transfer polymerization (GTP) of N,N-dimethylacrylamide (DMAA) promoted by bis(trifluoromethanesulfonyl)imide (Tf2NH), one of the strong Brønsted acids, which proceeded in a living fashion for the synthesis of polyacrylamides with well-defined structures.  The Tf2NH-promoted GTP of DMAA initiated by (Z)-1-(dimethylamino)-1-trimethylsiloxy-1-propene ((Z)-DATP), an amino silyl enolate, at 0 °C homogeneously proceeded to produce PDMAA with a predetermined molecular weight and a narrow molecular weight distribution.  The living nature of the polymerization was confirmed by the matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) analysis, kinetic measurements, and a post polymerization experiment.

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Notes

  1. 1.

    The theoretical molecular weight (M n,calcd) of PDMAA obtained from Tf2NH-promoted GTP was calculated by the following equation: M n,calcd = [M]0/([I]0−[Tf2NH]0) × conv. × (MW of DMAA = 99.13) + (MW of initiator residue = 101.15). According to the proposed mechanism of polymerization described in Ref. [25] the silyl enolate for the initiator must be consumed by the reaction with Tf2NH to produce the actual catalyst, Tf2NSiMe3. Thus, [Tf2NH]0 was subtracted from [I]0 in the equation to obtain the effective concentration of the initiator for the polymerization

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  1. Faculty of Engineering, Hokkaido University, Sapporo, Japan

    Keita Fuchise

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Fuchise, K. (2014). Precise Synthesis of Poly(N,N-Dimethylacrylamide) by Group Transfer Polymerization Using a Strong Brønsted Acid and an Amino Silyl Enolate. In: Design and Precise Synthesis of Thermoresponsive Polyacrylamides. Springer Theses. Springer, Tokyo. https://doi.org/10.1007/978-4-431-55046-4_3

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