α,ω-Di(glycerol carbonate) telechelic polyesters and polyolefins as precursors to polyhydroxyurethanes: an isocyanate-free approach

Liana Annunziata (1) , Abdou K. Diallo (1) , Stéphane Fouquay (2) , Guillaume Michaud (3) , Frédéric Simon (3) , Jean-François Carpentier (1) , Sophie M. Guillaume (1)

1 ISCR - Institut des Sciences Chimiques de Rennes
2 BOSTIK S.A
3 BOSTIK CRD

α,ω-Di(glycerol carbonate) telechelic poly(propylene glycol) (PPG), poly(ethylene glycol) (PEG), poly(ester ether) (PEE), and poly(butadiene) (PBD) have been synthesized through chemical modification of the corresponding α,ω-dihydroxy telechelic polymers (PPG-OH2, PEG-OH2, PEE-OH2 and PBD-OH2, respectively). Tosylation of the polymer diols with 4-tosylmethyl-1,3-dioxolan-2-one (GC-OTs) afforded, in high yields, the desired PPG, PEG, PEE and PBD end-capped at both termini with a five-membered ring cyclic glycerol carbonate (4-hydroxymethyl-1,3-dioxolan-2-one, GC). The GC-functionalization of the polymers at both chain-ends has been confirmed by NMR (1H, 13C, 1D and 2D) and FTIR spectroscopies. Using PPG-GC2 to demonstrate the concept, the corresponding polyhydroxyurethanes (PHUs/non-isocyanate polyurethanes (NIPUs)) have been subsequently prepared following a non-isocyanate method upon ring-opening catalyst-free polyaddition of the PPG-GC2 with JEFFAMINEs (Mn = 230-2000 g mol−1). The effect of various additives introduced during the polyaddition reaction has been studied at different temperatures. In particular, addition of LiBr (5 mol%) to the reaction medium was found to slightly promote the cyclocarbonate/amine reaction. The polymerization process was supported by FTIR and SEC analyses.

Mots clés: Diol; Glycerol carbonate; telechelic polymers; hydroxy telechelic polymers; non-isocyanate polyurethane (NIPU); poly(hydroxy urethane) (PHU); poly(ethylene glycol) (PEG); poly(propylene glycol) (PPG); poly(butadiene) (PBD); polyester

Domaines: Autre

Liana Annunziata, Abdou K. Diallo, Stéphane Fouquay, Guillaume Michaud, Frédéric Simon, et al.. α,ω-Di(glycerol carbonate) telechelic polyesters and polyolefins as precursors to polyhydroxyurethanes: an isocyanate-free approach. Green Chemistry, 2014, 16 (4), pp.1947-1956. ⟨10.1039/C3GC41821A⟩. ⟨hal-01067261⟩