Polymorphism of self-assembled colloidal nanostructures of comblike and bottlebrush block copolymers

We present a scaling theory describing equilibrium properties of starlike micelles formed by a diblock copolymer with bottlebrush (bb) blocks in solutions. In dilute and semidilute solutions, the blocks are envisioned as linear chains of impermeable superblobs with sizes D A and D B . Depending on the ratio of block "thicknesses", D A /D B , micelles can exhibit different power law dependences on solution concentration. We demonstrate that bb branching of blocks increases the number of different regimes in the diagram of states compared with diblock copolymers with linear blocks. In particular, in concentrated solution, thickness D A of soluble block A decreases and micelles rearrange similarly to spherical domains in melts of diblock copolymer with the concentrationdependent size of the monomer unit in the corona block. In both the semidilute and concentrated solutions, starlike micelles remain essentially impermeable and exhibit quasiglobular regimes. The theoretical predictions are contrasted to experiments.

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Architectural control over morphologies of bottlebrush block copolymer superstructures

Mikhailov,

Zhulina,

Borisov

et al. 2023

AIP Advances

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The morphology of superstructures formed by bottlebrush block copolymers in the melt can be tuned by changing the side chain length or/and their grafting density at constant volume fractions of the blocks. This feature enables fabrication of microphase separated bulk structures and mesoporous materials thereof with spherical or cylindrical domains (precursors of the mesopores), with high porosity unattainable for materials produced from conventional linear block copolymers. These paradigms are proven by DPD simulations that allow constructing morphological phase diagrams of the melt of block copolymers comprising one linear and one bottlebrush block and comparing the simulation results to the predictions of the mean field analytical theory. While the binodal lines separating the stability regions of spherical and cylindrical domains predicted by the theory perfectly match the simulation results, the simulation indicates appearance of a gyroid phase around the theoretical binodal separating the stability ranges of cylinders and lamellae. The results of our work provide guidelines for macromolecular design of novel composite and mesoporous materials with a wide spectrum of potential applications.

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Polymorphism of self-assembled colloidal nanostructures of comblike and bottlebrush block copolymers

Cited by 3 publications

References 34 publications

Amphiphilic comb-block copolymers synthesized by photoinitiated polymerization for stabilization of oil–water emulsion by solution self-assembly

Amphiphilic comb-block copolymers synthesized by photoinitiated polymerization for stabilization of oil–water emulsion by solution self-assembly

Solutions of Diblock Copolymer Micelles with Bottlebrush Blocks. Scaling Model

Architectural control over morphologies of bottlebrush block copolymer superstructures

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