New catalysis for fast bulk ring-opening polymerization of lactide monomers

Abstract

The ring-opening polymerization of lactides has been studied in bulk using either 2-ethylhexanoic acid tin(II) salt, Sn(Oct)2, or aluminum triisopropoxide, Al(OiPr)3, as the initiator over a wide range of temperature and monomer-to-initiator molar ratio. A high increase in the bulk polymerization rate has been observed when the initiator was added with an equimolar amount of a Lewis base, such as triphenylphosphine (P(φ)3) and 4-picoline (C6H7N) added to Sn(Oct)2 and Al(OiPr)3, respectively. Melt stable polylactides of high molecular weight and reasonably narrow molecular weight distribution have been accordingly prepared. The use of the Sn(Oct)2.P(φ)3 equimolar combination has allowed for reaching an acceptable balance between propagation and depolymerization rates, so that the polymerization is fast enough to be performed through a continuous single-stage process in a twin-screw extruder. A global activation mechanism is proposed and discussed by comparison with both investigated initiation systems.