Block Copolymers of Macrolactones/Small Lactones by
a “Catalyst-Switch” Organocatalytic Strategy. Thermal
Properties and Phase Behavior
Posted on 2018-03-16 - 19:49
Poly(macrolactones)
(PMLs) can be considered as biodegradable
alternatives of polyethylene; however, controlling the ring-opening
polymerization (ROP) of macrolactone (ML) monomers remains a challenge
due to their low ring strain. To overcome this problem, phosphazene
(t-BuP4), a strong superbase, has to be
used as catalyst. Unfortunately, the one-pot sequential block copolymerization
of MLs with small lactones (SLs) is impossible since the high basicity
of t-BuP4 promotes both intra- and intermolecular
transesterification reactions, thus leading to random copolymers.
By using ROP and the “catalyst-switch” strategy [benzyl
alcohol, t-BuP4/neutralization with diphenyl
phosphate/(t-BuP2)], we were able to synthesize
different well-defined PML-b-PSL block copolymers
(MLs: dodecalactone, ω-pentadecalactone, and ω-hexadecalactone;
SLs: δ-valerolactone and ε-caprolactone). The thermal
properties and the phase behavior of these block copolymers were studied
by differential scanning calorimetry and X-ray diffraction spectroscopy.
This study shows that the thermal properties and phase behavior of
PMLs-b-PSLs are largely influenced by the PMLs block
if PMLs components constitute the majority of the block copolymers.
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Ladelta, Viko; Kim, Joey D.; Bilalis, Panayiotis; Gnanou, Yves; Hadjichristidis, Nikos (2018). Block Copolymers of Macrolactones/Small Lactones by
a “Catalyst-Switch” Organocatalytic Strategy. Thermal
Properties and Phase Behavior. ACS Publications. Collection. https://doi.org/10.1021/acs.macromol.8b00153
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AUTHORS (5)
VL
Viko Ladelta
JK
Joey D. Kim
PB
Panayiotis Bilalis
YG
Yves Gnanou
NH
Nikos Hadjichristidis