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. 2021 May 17;13(10):1627.
doi: 10.3390/polym13101627.

Synthesis of Dense 1,2,3-Triazole Polymers Soluble in Common Organic Solvents

Shota Yamasaki  1 , Yuri Kamon  1 , Linlin Xu  1 , Akihito Hashidzume  1
Affiliations

Synthesis of Dense 1,2,3-Triazole Polymers Soluble in Common Organic Solvents

Shota Yamasaki et al. Polymers (Basel). .

Abstract

Aiming at synthesis of dense 1,2,3-triazole polymers soluble in common organic solvents, a new 3-azido-1-propyne derivative, i.e., t-butyl 4-azido-5-hexynoate (tBuAH), was synthesized and polymerized by copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) and Huisgen cycloaddition (HC). CuAAC polymerization produced poly(tBuAH) composed of 1,4-disubstituted 1,2,3-triazole units (1,4-units), whereas HC polymerization gave poly(tBuAH) composed of 1,4- and 1,5-disubstituted 1,2,3-triazole units (1,4- and 1,5-units). In HC polymerization, the fraction of 1,4-unit (f1,4) decreased with the permittivity of solvent used. Differential scanning calorimetry data indicated that the melting point of poly(tBuAH) increased from 61 to 89 °C with increasing f1,4 from 0.38 to 1.0, indicative of higher crystallinity of poly(tBuAH) composed of 1,4-unit. Preliminary steady-state fluorescence study indicated that all the poly(tBuAH) samples of different f1,4 emitted weak but significant fluorescence in DMF. The maximum of fluorescence band shifted from ca. 350 to ca. 450 nm with varying the excitation wavelength from 300 to 400 nm.

Keywords: 1,2,3-triazole; Huisgen cycloaddition polymerization; copper(I)-catalyzed azide–alkyne cycloaddition polymerization; t-butyl 3-azide-6-hexynoate.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Synthesis (a) and polymerization of tBuAH (b).
Figure 1
Figure 1
1H NMR spectra for tBuAH (a) and poly(tBuAH) obtained by CuAAC polymerization (b) and HC polymerization (DMSO-d6) (c). The black and green curves are spectra and integrals, respectively.
Figure 2
Figure 2
Expanded 1H NMR for poly(tBuAH) samples obtained by HC polymerization using DMF (a), THF (b), and toluene as solvent (DMSO-d6) (c). The black and green curves are spectra and integrals, respectively.
Figure 3
Figure 3
DSC data for the poly(tBuAH) samples of different f1,4 under a stream of nitrogen (200 mL min−1); the first (a) and second heating scans (b). The heating rate was set at 10 °C min−1.
Figure 4
Figure 4
Steady-state fluorescence spectra for 1.0 g L−1 solutions of the poly(tBuAH) samples of different f1,4 in DMF obtained by excitation at varying wavelengths from 300 to 400 nm; f1,4 = 1.0 (a), 0.49 (b), 0.46 (c), and 0.38 (d).
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