Alternating poly(lactic acid)/poly(ethylene-co-butylene) supramolecular multiblock copolymers with tunable shape memory and self-healing properties

Abstract

Alternating supramolecular multiblock copolymers with hard poly(lactic acid) (PLA) and soft poly(ethylene-co-butylene) (PEB) segments were prepared by terminal functionalization of PLA–PEB–PLA triblock oligomers with the 2-ureido-4[1H]-pyrimidinone (UPy) self-complementary quadruple hydrogen bonding units. Such supramolecular copolymers (SMPs) exhibit the characteristic properties of thermoplastic elastomers. The thermal, morphological, mechanical, shape memory, and self-healing properties of SMPs can be readily modulated by varying the composition, stereostructure, and crystallizability of PLA blocks. The prepared SMPs are shown as transparent and elastic films, while their PLA–PEB–PLA precursors are viscous or brittle solids. Crystallization of isotactic PLA blocks, i.e. poly(L-lactic acid) (PLLA), in SMPs is significantly impeded by the end-caped UPy motifs. The prepared SMPs show a well-defined microphase-separated structure, which varies from cylindrical to lamellar morphology with the increasing fraction of PLA blocks. Compared to the PLA–PEB–PLA precursors, SMPs exhibit improved mechanical strengths, modulus, elongation-at-break, good thermally-induced shape memory and light-triggered self-healing properties. The recovery ratios of SMPs containing atactic poly(D,L-lactic acid) (PDLLA) blocks are nearly 100%. The shape memory and self-healing properties of SMPs can be modulated by the stereostructure of PLA segments and they become worse when the isotactic, crystallizable PLLA segments are presented.