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Unsaturated oligoesters containing internal triple and double bonds based on DL-malic acid: synthesis, characterization and study of crosslinking via click reaction

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Abstract

Unsaturated polyesters are of interest to scientists due to the presence of modifiable functional groups such as double and triple bonds. Active sites in the unsaturated polyesters are special options for drug delivery and biomedical applications. Click reaction is an attractive way to transfer drugs using unsaturated polyesters. In this study, low molecular weight unsaturated aliphatic polyesters containing internal triple and double bonds based on DL-malic acid have been synthesized. Oligoesters with different degrees of unsaturation have been synthesized by condensation polymerization of DL-malic acid and 1,4-butanediol, cis-2-butene-1,4-diol, 2-butyne-1,4-diol, and diol mixtures. Polymerization was performed in the absence of catalyst and at low temperature (130 °C) by bulk polymerization. FT-IR, 1H-NMR, 13C-NMR, and GPC analyses were used for the characterization of the synthesized structures. The thermal properties of the oligoesters were investigated using DSC analysis. The glass transition temperatures for unsaturated oligoesters containing single, double, and triple bonds were obtained -32 °C, -24 °C, and -38 °C, respectively. 1H-NMR spectra showed that DL-malic acid self-condensation reaction in the presence of 2-butyne-1,4-diol, cis-2-butene-1,4-diol, and 1,4-butanediol monomers occurs ~ 8%, ~ 5%, and ~ 4%, respectively. The HOMO–LUMO gap of DL-malic acid (7.0145 eV) and 2-butyne-1,4-diol (6.3905 eV) were calculated using DFT computational method at the base level of B3LYP/6-311G + (d,p). Oligoester containing internal triple bonds (2-butyne-1,4-diol (ByD50)) were crosslinked with 1,4-diazidobutane, and reaction progress was followed by FT-IR analysis. Unlike isocyanate curing, azide curing is not sensitive to moisture. It is hoped that unsaturated polyesters containing triple bonds can be used in click reactions and polyester modification. Oligoester contains a triple bond (ByD50) suitable for drug delivery. These oligoesters have a controllable degree of crosslinking and can be used to modify an oligoester with a controllable degree.

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Acknowledgements

The authors are grateful to the Malek Ashtar University of Technology for supporting this work.

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  1. Faculty of Chemistry and Chemical Engineering, Malek Ashtar University of Technology, Tehran, Iran

    Dariush Fallah, Reza Fareghi-Alamdari & Saeed Tavangar

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  1. Dariush Fallah
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Correspondence to Reza Fareghi-Alamdari.

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Fallah, D., Fareghi-Alamdari, R. & Tavangar, S. Unsaturated oligoesters containing internal triple and double bonds based on DL-malic acid: synthesis, characterization and study of crosslinking via click reaction. J Polym Res 29, 458 (2022). https://doi.org/10.1007/s10965-022-03218-9

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