Reinvestigation of the mechanism of polymerization of β-butyrolactone from 1, 5, 7-triazabicyclo[4.4.0]dec-5-ene. Issue 14 (14th March 2018)

• Record Type: Journal Article
• Authors: Moins, S.; Henoumont, C.; De Winter, J.; Khalil, A.; Laurent, S.; Cammas-Marion, S.; Coulembier, O.
• Is Part Of: Polymer chemistry. Volume 9:Issue 14(2018)
• Page Start: 1840
• Page End: 1847
• Publication Date: 2018-03-14
• Subjects: Polymers -- Periodicals; Macromolecules -- Periodicals; Polymerization -- Periodicals; 547.705
• DOI: 10.1039/c8py00206a
• Languages: English
• ISSNs: 1759-9954

Abstract

Abstract : The questionable mechanism initially proposed to explain how 1, 5, 7-triazabicyclo[4.4.0]dec-5-ene (TBD) allows us to ring-open β-lactones, such as β-butyrolactone (BL), is reinvestigated here. Abstract : The questionable mechanism initially proposed to explain how 1, 5, 7-triazabicyclo[4.4.0]dec-5-ene (TBD) allows us to ring-open β-lactones, such as β-butyrolactone (BL), is reinvestigated here. With the use of a trisubstituted β-lactone, i.e. ( R, S )-benzylcarbonyl-3, 3-dimethyl-2-oxetanone, and the association of techniques such as 1 H/DOSY NMR and MALDI/ESI-MS, we demonstrated that BL is effectively polymerized by the TBD in bulk at 60 °C, minorly from the reported N -acyl-α, β-unsaturated TBD species, and majorly from crotonate anions issued from the basic activation of BL. In contrast to what has been reported, the TBD is not covalently linked to the PBL chain but mainly plays the role of a counterion in the –C(O)O −, TBDH + active site.