Tetracrystalline Tetrablock Quarterpolymers: Four Different Crystallites under the Same Roof

Abstract

Multicrystalline block copolymers having three or more crystalline segments are essential materials for the advancement of physics in the field of crystallinity. Due to the challenging synthesis of multicrystalline polymers only a limited number of tricrystalline terpolymers are reported until now. We report, for the first time, the synthesis of poly(ethylene)-b-poly(ethylene oxide)-b-poly(εcaprolactone)-b-poly(L-Lactide) (PE-b-PEO-b-PCL-b-PLLA) tetracrystalline tetrablock quarterpolymer, by combining polyhomologation,ring-opening polymerization, and an organic/metal "catalyst switch" strategy. 1 H NMR spectroscopy and gel-permeation chromatography confirm the formation of the tetrablock quarterpolymer, while differential scanning calorimetry, Xray diffraction, and wide-line separation solid-state NMR spectroscopy reveal the existence of four different crystalline domains.

Polyether-Based Block Co(ter)polymers as Multifunctional Lubricant Additives

“…Such issues can be overcome by employing organocatalytic ROP. − One of the most promising organic catalysts is triethyl borane (TEB)/phosphazene base t -BuP 2 (Lewis pair). This Lewis pair promotes living/controlled organocatalytic ROP of epoxides at ambient conditions toward well-defined and metal-free polyether (co)­polymers. − …”