Hierarchical Self-Assembly of Supramolecular Double-Comb Triblock Terpolymers

Abstract

Involving supramolecular chemistry in self-assembling block copolymer systems enables design of macromolecular architectures that are challenging to obtain through conventional all-covalent routes. In this work we present supramolecular double-comb triblock terpolymers in which both outer blocks are able to interact with a surfactant via hydrogen bonding and thereby form a comb-shaped architecture upon complexation. While the neat triblock terpolymer only formed a triple lamellar morphology, multiple hierarchical structures were observed in these supramolecular comb–coil–comb triblock terpolymers by simply adjusting the surfactant concentration. Structures included spheres on tetragonally packed cylinders-in-lamellae and spheres on double parallel lamellae-in-lamellae, as evidenced by electron microscopy and X-ray scattering. Incorporation of a middle coil block thus allowed an even higher macromolecular complexity than the previously reported double-comb diblock copolymers.

Order–disorder transition in supramolecular polymer combs/brushes with polymeric side chains

“…The urethane peak at 4.86 ppm shows that the coupling occurred successfully. Furthermore, 13 C NMR proved the coupling, although the low solubility of 10 and 12 hindered the analysis and some peaks showed a low signal to noise ratio ( Fig. S9 and S11 †).…”

“…In polymer science, more recently, a few researchers coined the terms supramolecular graft/comb/brush polymer. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] These reversible comb-shaped polymers can dissociate depending on the strength of the used supramolecular entity (sticker) at different temperatures. 4 Moreover, the second parameter influencing the association is the steric hindrance of the side chains in highly grafted polymers, which can lead to significant chain stretching.…”

“…Telechelic supramolecular polymers and comb polymers with short side-groups were discussed extensively in the past. 4,9,[12][13][14][26][27][28][29][30] Therefore, in our design, the focus is on the synthesis and self-assembly of novel supramolecular polymers with long ( polymeric) sidebranches. Dalcanale et al recently introduced a new sticker, namely…”

Self‐Assembly of Multiblock Copolymers

“…A complete transformation to lamella‐lamellae morphology occurred above a molar loading of 75 %. Supramolecular modification can be expanded to more than one block as demonstrated on the self‐assembly of P4VP‐ b ‐PS‐ b ‐PAPI (PAPI=poly( N ‐acryloylpiperidine)) in the presence of 3‐nonadecylphenol (3‐NDP) . The two terminal blocks are hydrogen bond acceptors and bind 3‐NDP to give supramolecular comb‐coil‐comb triblock terpolymers that show different chain packing and morphologies as compared to the unmodified triblock terpolymer.…”

“…Supramolecular modification can be expanded to more than one block as demonstrated on the self-assembly of P4VP-b-PS-b-PAPI (PAPI = poly(N-acryloylpiperidine)) in the presence of 3-nonadecylphenol (3-NDP). [57] The two terminal blocks are hydrogen bond acceptors and bind 3-NDP to give supramolecular comb-coil-comb triblock terpolymers that show different chain packing and morphologies as compared to the unmodified triblock terpolymer. The morphologies exhibit a hierarchical structure, where the supramolecular additive organizes into few-nanometer-sized structures within the microdomains of the polymer morphology.…”