Issue 10, 2011

Phosphoric and phosphoramidic acids as bifunctional catalysts for the ring-opening polymerization of ε-caprolactone: a combined experimental and theoretical study

Abstract

The ring-opening polymerization of ε-caprolactone catalyzed by the phosphoric acid (PhO)2P(O)OH (PA) or the phosphoramidic acid (PhO)2P(O)NH(SO2CF3) (PAA) has been investigated experimentally and computationally. The two catalysts promote polymerization under mild conditions, with PAA being slightly more active than PA. The controlled character of the polymerization has been examined thoroughly, and the polymerization conditions were optimized so as to afford well-defined polycaprolactones of molar masses up to 15 000 g mol−1 and narrow molar mass distributions. Density Functional Theory calculations support a bifunctional mechanism for these organo-catalyzed ROPs, with participation of both the acidic proton and basic P[double bond, length as m-dash]O (/S[double bond, length as m-dash]O) moiety of the phosphoric and phosphoramidic acids.

Graphical abstract: Phosphoric and phosphoramidic acids as bifunctional catalysts for the ring-opening polymerization of ε-caprolactone: a combined experimental and theoretical study

Supplementary files

Article information

Article type
Paper
Submitted
12 May 2011
Accepted
17 Jun 2011
First published
29 Jul 2011

Polym. Chem., 2011,2, 2249-2256

Phosphoric and phosphoramidic acids as bifunctional catalysts for the ring-opening polymerization of ε-caprolactone: a combined experimental and theoretical study

D. Delcroix, A. Couffin, N. Susperregui, C. Navarro, L. Maron, B. Martin-Vaca and D. Bourissou, Polym. Chem., 2011, 2, 2249 DOI: 10.1039/C1PY00210D

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