Synthesis and Self-Assembly of Well-Defined Star and Tadpole Homo-/Co-/Terpolymers

Abstract

Tadpole polymers are excellent candidates to explore how architecture can influence self-assembly because they combine two topologies in the same molecule (ring polymer as the head and linear polymer as the tail). In this work, we synthesize well-defined tadpole homo-/co-/terpolymers derived from the appropriate chemical modification reactions of the corresponding 3-miktoarm star homo-/co-/ terpolymers via anionic polymerization, high vacuum techniques, and chlorosilane chemistry in combination with the Glaser coupling reaction. The 3-miktoarm star homo-/ co-/terpolymers bear two arms with t-butyl dimethylsiloxypropyl functional end-groups, whereas after deprotection, the ωhydroxyl chain-ends were modified to alkyne moieties. The dialkyne star polymers in the presence of Cu(I)Br and N,N,N′,N″,N″-pentamethyldiethylenetriamine were then transformed to well-defined tadpole homo-/co-/terpolymers. We employed strongly immiscible blocks to enable characterization using electron microscopy and X-ray scattering to explore how the molecular topology influences the self-assembled bulk-state microdomain morphologies.

Alternating Gyroid Network Structure in an ABC Miktoarm Terpolymer Comprised of Polystyrene and Two Polydienes

“…The synthesis procedure involved a combination of anionic polymerization, polyhomologation and linking reactions. The same group has been pursuing star terpolymers of various types involving ABC nonlinear architectures as evident by recent publications without observing three-dimensional cubic structure in such complex architecture terpolymers [51,52].…”

Threading-Induced Dynamical Transition in Tadpole-Shaped Polymers

“…We dub these architectures “chimeric,” the name given to any mythical animal formed from parts of various other animals (Figure A). The simplest example of a chimeric architecture is that of a tadpole-shaped polymer, “tadpole” for brevity (see Figure B,C), which has recently been realized experimentally , and has attracted considerable attention in the field of protein folding. , …”

“…Our results suggest that even a modest polymer mass can display a broad dynamical range and this property can be harnessed to keep the costs low while achieving the desired rheology through informed polymer design. Our work might therefore serve to motivate future theoretical and experimental characterizations of entangled solutions of higher-order chimeric structures which may be now feasibly realized via synthetic chemistry ,, or DNA origami.…”

Triply Helical Giant Domain with Homochirality in a Terpolymer Blend System

“…Furthermore, the induction of selective conformational chirality into achiral block copolymers by the addition of small chiral molecules was reported, and the successive formation of chiral arrangements of Au nanoparticles in block copolymer films was confirmed . Another featured helical morphology was found in a poly­(isoprene- b -styrene- b -2-vinylpyridine) (PI-PS-P2VP) star-branched terpolymer …”

“…30 Another featured helical morphology was found in a poly(isoprene-b-styrene-b-2vinylpyridine) (PI-PS-P2VP) star-branched terpolymer. 31 Recently, morphological studies on block polymer selfassembly have been extended to tetrablock terpolymers of the A 1 BA 2 C type, which include two A component chains with different conformations; i.e., A 1 should reveal a tail conformation, while A 2 adopts a bridge conformation. The self-assembly of this type of complex molecular architecture has been actively studied both experimentally and theoretically.…”