Multicompartment Microparticles of SBT Triblock Terpolymers through 3D Confinement Assembly

Abstract

Self-assembly of block copolymers in three-dimensional (3D) soft confinement has become a versatile method for the preparation of functional microparticles. While the morphological behavior of AB diblock copolymers in confinement is fairly well understood, only sporadic examples exist for ABC triblock terpolymers. Considering the more complex morphological space of terpolymers, a better understanding of their behavior in confinement would be desirable to gain access to a large variety of multicompartment microparticles (MMs). Here, we report on the 3D confinement self-assembly of MMs from a library of polystyrene-blockpolybutadiene-block-poly(tert-butyl methacrylate) (PS-b-PB-b-PT or SBT) triblock terpolymers with widely different block volume fractions (ϕ), which can be mapped into a ternary microphase diagram. Equal-sized end blocks (ϕ S ≈ ϕ T ) result in MMs with lamella−lamella (LL) morphology and a tulip-bulb or pinecone shape, irrespective of ϕ B . For asymmetric end blocks (ϕ S > ϕ T ) at low ϕ B , prolate ellipsoids develop a hexagonally packed core−shell ring (HCR) morphology, which changes with increasing ϕ B to a transition structure between HCR and a concentric sphere-in-lamella (CSL) morphology. Further increasing ϕ B to ϕ S ≈ ϕ B at low ϕ T , the structure transforms entirely to CSL in an onion-like shape. Selective cross-linking of the PB middle block and disassembly of the MMs give access to a variety of nanostructures such as core−shell rings, Janus nanobowls, and nanocups.

Transformable Colloidal Polymer Particles with Ordered Internal Structures

“…[ 1–8 ] A 3D confined assembly of block copolymers (BCPs) that enables the generation of internally ordered colloidal particles with various shapes has received increasing attentions in the last two decades. [ 9–18 ] In particular, lots of efforts have been paid to an emulsion solvent evaporation‐induced 3D soft confined assembly. [ 19–26 ] Attributed to the deformable shape, adjustable size, and boundary conditions, emulsion droplets enable flexible designing for the morphology of BCP colloidal particles.…”

“…[1][2][3][4][5][6][7][8] A 3D confined assembly of block copolymers (BCPs) that enables the generation of internally ordered colloidal particles with various shapes has received increasing attentions in the last two decades. [9][10][11][12][13][14][15][16][17][18] In particular, lots of efforts have been paid to an emulsion solvent evaporation-induced Based on studies combining experiments and simulations, internally ordered colloidal particles that are able to undergo morphological transformations both in shape and internal structure are presented. The particles are prepared by emulsion solvent evaporation-induced 3D soft confined assembly of diblock copolymer polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP).…”

Chiral transfer‐dictated self‐assembly of chiral block copolymers

“…[147][148][149] As for 3D confinement, the microphase separation occurs in a spherical, spheroidal, or polyhedral space (e.g., evaporative emulsion droplets, spherical pores). [139,150,151] As a synergistic outcome of above impacts, chiral structures were formed from the 2D and 3D confined assembly of achiral BCPs, including single/double/multiple helixes and spirals. [148,[152][153][154][155][156][157][158][159][160][161][162][163][164][165][166][167][168][169][170] Although these examples differed from each other, demanding different requirements to form the chiral structures, a high incommensurability between D and L 0 was usually mandatory, that is, a non-integral D/L 0 value.…”

Responsive Colloidal Polymer Particles with Ordered Mesostructures

“…systematically studied the 3D soft confinement assembly of polystyrene‐ b ‐polybutadiene‐ b ‐poly(tert‐butyl methacrylate) (PS‐ b ‐PB‐ b ‐PtBMA) into colloidal particles with a variety of ordered mesostructures, including Matryoshka structures, [ 48 ] ellipsoidal particles with stacked PB‐ring microdomains, [ 49 ] and other morphologies depending on the block volume fractions ( Figure ). [ 50 ] Moreover, the 3D soft confinement assembly of PS‐ b ‐P4VP‐ b ‐PtBMA was investigated, where the volume fraction was adjusted by supramolecular additives, hydrogen, or halogen bond donors, and the P4VP‐block. [ 51 ] For example, a halogen bond donor, that is, cholesteryl hemisuccinate, not only changed the phase morphology of the P4VP‐microdomains from spherical to lenticular, but also the overall morphology of the colloidal particle from onion‐ to pupa‐like.…”