Macromolecular Rapid Communications 2012-11-23

Controlled ROP of β-butyrolactone simply mediated by amidine, guanidine, and phosphazene organocatalysts.

Cédric G Jaffredo, Jean-François Carpentier, Sophie M Guillaume

Index: Macromol. Rapid Commun. 33(22) , 1938-44, (2012)

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Abstract

Basic organocatalysts of the guanidine (1,5,7-triazabicyclo[4.4.0]dec-5-ene, TBD), amidine (1,8-diazabicyclo[5.4.0]-undec-7-ene, DBU), and phosphazene (2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2diazaphosphorine, BEMP) type do effectively polymerize β-butyrolactone (BL). Poly(3-hydroxybutyrate)s (PHBs) with controlled molecular features, that is, controlled molar masses, narrow molar mass distributions, and well-defined functional end groups are thus formed at 60 °C from bulk monomer, with M(n,NMR) up to 21 500 g mol(-1). The formation of α,ω-guanidine/amidine/phosphazene,crotonate functionalized PHBs, as demonstrated by NMR, SEC, and MALDI-ToF mass spectrometry analyses, mechanistically suggests the formation of N-acyl-α,β-unsaturated propagating species that originate from 1:1 guanidine/amidine/phosphazene:BL adducts.Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.