Issue 9, 2020

Zinc diethyldithiocarbamate as a catalyst for synthesising biomedically-relevant thermogelling polyurethanes

Abstract

Zinc dithiocarbamates are traditionally highly-efficient catalysts for accelerating rubber vulcanization reactions, but have thus far not found substantial use in other forms of polymerisations. Herein, we demonstrate a new application of zinc diethyldithiocarbamate (ZDTC) for the synthesis of polyurethanes suitable for biomedical applications. Compared with other organozinc compounds such as zinc acetylacetonate and zinc neodecanoate, ZDTC showed exceptional catalytic performance, capable of forming high molecular weight polyurethanes, with the reaction tolerant to different organic solvents. The ZDTC-catalysed biocompatible amphiphilic polyurethanes comprising PEG and PPG blocks form thermo-responsive hydrogels which showed remarkably low sol-to-gel transition temperatures at surprisingly low concentrations in water. Microstructural analysis of the polyurethane aqueous solutions by small-angle X-ray scattering (SAXS) experiments revealed considerable supramolecular self-assembly of the polyurethanes even at 4 °C. Valuably, cell viability studies revealed that residual ZDTC catalysts present in unpurified polyurethane polymers exerted considerably lower cytotoxicities than those catalysed by tin(IV) catalysts such as dibutyltin dilaurate (DBTL). As demonstrated herein, ZDTC may be a possible alternative to highly-toxic organotin catalysts for the synthesis of polyurethanes, with further potential for other polymerization reactions reliant on organotin Lewis acidity such as polyester synthesis.

Graphical abstract: Zinc diethyldithiocarbamate as a catalyst for synthesising biomedically-relevant thermogelling polyurethanes

Supplementary files

Article information

Article type
Paper
Submitted
24 Sept. 2020
Accepted
28 Okt. 2020
First published
28 Okt. 2020
This article is Open Access
Creative Commons BY license

Mater. Adv., 2020,1, 3221-3232

Zinc diethyldithiocarbamate as a catalyst for synthesising biomedically-relevant thermogelling polyurethanes

J. Y. C. Lim, Q. Lin, C. K. Liu, L. Guo, K. Xue and X. J. Loh, Mater. Adv., 2020, 1, 3221 DOI: 10.1039/D0MA00734J

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