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Ring-opening polymerisation of ɛ-caprolactone catalysed by Brønsted acids

Li-Hui Yao, Shuang-Xi Shao, Lan Jiang, Ning Tang, and Jin-Cai Wu

Institute of Materials Engineering, Ningbo University of Technology, Ningbo, 315016, China



Abstract: Two new Brønsted acids [2,2′-ethylidene-bis (4,6-di-tert-butylphenol)] phosphoric acid (EDBPPOOH) and (3,3′,5,5′-tetra-tert-butylbiphenyl-2,2′-diol) phosphoric acid (TBPO-POOH) were synthesised and fully characterised by 1H NMR and 13C NMR spectra and mass spectra. The ringopening polymerisation (ROP) of ɛ-caprolactone (ɛ-CL) catalysed by the two Brønsted acids proceeded at 110°C without a solvent or at ambient temperature in toluene. Experimental results indicated that the two Brønsted acids were efficient catalysts for the ROP of ɛ-CL with moderate number-average molar mass (Mn) and narrow polydispersity indices (PDI). The catalytic activity of TBPO-POOH is higher than EDBP-POOH in the ROP of ɛ-CL. After benzyl alcohol was added, it was able to accelerate the polymerisation process. The polymerisation can also occur with the addition of water with a monomer/catalyst/initiator mole ratio of 100: 1: 1. The living polymerisation was ascertained by the linear relationships of the Mn vs. monomer conversion, then it was further confirmed by a second-feed experiment of a double monomer producing double Mn. A kinetic study of the relationships between monomer concentration and time revealed a first-order dependence on monomer concentration in the polymerisation. End-group analysis of 1H NMR spectra and electrospray-ionisation mass spectra suggests that the two Brønsted acids are capable of catalysing and initiating the ROP of ɛ-CL.

Keywords: Brønsted acids – ring-opening polymerisation – ɛ-caprolactone – living polymerisation – first-order reaction

Full paper is available at

DOI: 10.2478/s11696-014-0585-z


Chemical Papers 68 (10) 1381–1389 (2014)

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