Ultrafast Self-Assembly of Bottlebrush Statistical Copolymers: Well-Ordered Nanostructures from One-Pot Polymerizations

Fei, Hua‐Feng; Yavitt, Benjamin M.; Nuguri, Sravya; Yu, Yong‐Guen; Watkins, James J.

doi:10.1021/acs.macromol.1c01311

Cited by 11 publications

(22 citation statements)

References 52 publications

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“…The steric hindrance-induced stiffness of the backbone can be incorporated by modeling it as a wormlike chain. 59,76 The fixed contour length allows the wormlike chain to handle highly extended conformations; 59 thus, the semiflexibility of the backbone is introduced by imposing a harmonic angle potential between the adjacent bonds (11) where θ 0 is the equilibrium angle and is set as π. The potential strength k a dictates the rigidity of the backbone, and k a = 0, 2, and 10 are considered in this work.…”

Section: ■ Model and Methodsmentioning

confidence: 99%

Hierarchical Self-Assembly of ABC-Type Bottlebrush Copolymers

et al. 2023

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We have performed dissipative particle dynamics simulations to study the self-assembly of ABC-type bottlebrush copolymers (BBCPs), one portion of whose backbone is grafted by pairs of A-blocks and the other portion is grafted by B/C-blocks in pairs, focusing on the effects of the number of A side chains, the length of B side chains relative to that of C side chains, and the rigidity of the backbone on the formation of hierarchical structures. A number of hierarchical structures with the superstructures formed by the phase separation between A and B/C-blocks and the substructures formed by the phase separation between B and Cblocks are observed. Some hierarchical structures are similar to those self-assembled by ABC star copolymers, whereas their stable parameter regions of ABC-type BBCPs are much larger. On the other hand, the ABC-type BBCPs can also form some novel hierarchical structures that are hard to form in ABC star copolymers. Though the formation of the A-superstructure and the B-substructure in many hierarchical structures can be independently controlled, there are also some hierarchical structures in which the transitions of the superstructure and substructures are coupled. In other words, the A-superstructure changes along with the transformation of the B-substructure for fixed f A . In addition, our results demonstrate that the rigidity of the backbone has a significant effect on the formation of the hierarchical structure in ABC-type BBCPs, i.e., a rigid backbone favors the normal arrangement of B-substructures to A-superstructures. Our work not only deepens the understanding of the self-assembly mechanism of ABC-type BBCPs but also provides helpful guidance for experiments to fabricate interesting hierarchical structures.

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Section: ■ Model and Methodsmentioning

confidence: 99%

Hierarchical Self-Assembly of ABC-Type Bottlebrush Copolymers

et al. 2023

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“…Among a series of recently developed synthetic strategies, ring‐opening metathesis polymerization (ROMP) based graft‐through synthesis emerged as a facile method for the mGBCP preparation [11c, 13] . In this method, different norbornene‐monofunctionalized linear macromonomers can be randomly copolymerized to form an A‐ ran ‐B type mGBCP with a target A/B ratio [11b,c, 12] . The living polymerization nature of ROMP produces a chain‐extendable A‐ ran ‐B macroinitiator for the synthesis of an (A‐ ran ‐B)‐ b ‐C mGBCP by adding a third macromonomer C at the end of the A/B copolymerization.…”

Section: Methodsmentioning

confidence: 99%

Rapid Access to Diverse Multicomponent Hierarchical Nanostructures from Mixed‐Graft Block Copolymers

Liang

Song

et al. 2022

Angewandte Chemie

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Multicomponent nanostructured materials assembled from molecular building blocks received wide attention due to their precisely integrated multifunctionalities. However, discovery of these materials with desirable composition and morphology was limited by their low synthetic scalability and narrow structural tuning window with given building blocks. Here, we report a scalable and diversity-oriented synthetic approach to hierarchically structured nanomaterials based on a few readily accessible building blocks. Mixed-graft block copolymers containing sequence-defined side chains were prepared through ring-opening metathesis copolymerization of three or four types of macromonomers. Intramolecularly defined interfaces promoted the formation of ordered hierarchical structures with lattice sizes tunable across multiple length scales. The same set of macromonomers were arranged and combined in different ways, providing access to diverse morphologies in the resultant structures.A holy grail in materials design is to construct synthetic materials with diverse functions using a limited set of building blocks that can be readily accessed. Biological systems covalently assemble canonical monomer building blocks, e.g., nucleic acids and amino acids, to biomacromolecules that exhibit a broad array of functions. Despite the

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“…Compared with diblock copolymer systems, multiblock copolymer systems possess additional composition and interaction parameters as well as adjustable segment sequences, − which can substantially affect the self-assembly process and increase the complexity of their phase separation. − Thereby, using triblock copolymers rather than diblock copolymers as structure-directing agents provides more opportunities for creation of novel mesoporous materials and exhibits easier access to bicontinuous network structures with the triply periodic hyperbolic-surface structures, − noncentrosymmetric structures, hierarchical mesostructures, bilayer perforated lamellae, − novel helical structures, and so on. To date, apart from Pluronic triblock copolymers, many tailor-made ternary amphiphilic block copolymer systems have also been developed for preparing mesoporous materials with various compositions based on their unique self-assembly behavior.…”

Section: Introductionmentioning

confidence: 99%

Pyrrole-Containing ABA Triblock Brush Polymers as Dual Functional Molecules to Facilely Access Diverse Mesostructured Materials

Wang

Gao

et al. 2022

Macromolecules

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We report a new type of ABA-type brush-like triblock copolymer (PEGMA-b-PPHMA-b-PEGMA), which is characterized by two hydrophilic end segments (A) and a hydrophobic midblock (B) bearing polymerizable pyrrole moieties. This kind of symmetric triblock copolymers can not only serve as a structure-directing agent for the formation of mesoporous silicates but also function as a polymerizable monomer or carbon source for further chemical conversion to deliver mesostructured polymer or carbon materials within the preformed silicate framework. By utilizing such dual functional macromolecules, rich morphologies of mesostructures are accessible through microphase separation, and the order−order transition among cubic, lamellar, 2D hexagonal, and bicontinuous mesostructures is sensitively achievable by varying the hydrophilic volume fraction of copolymers and TEOS dosage. These features enable facile access to diverse mesostructured silica, polymer, and carbon materials. Remarkably, due to the brush-like polymer architecture and the formation of loop configuration, a widely tunable pore size from mesoscale to macroscale is realizable through using a relatively lower molecular weight copolymer. Importantly, it is found that the brush-like hydrophilic segments of our triblock copolymers can firmly anchor into the silica walls without appreciable escape of copolymer template in commonly used solvents even under reflux extraction, providing a prerequisite for reliable confined chemical transformation into mesostructured polymer and carbon materials. Our work demonstrates that the design and synthesis of functional amphiphilic block copolymers will bring great opportunity for the development of novel mesostructured materials.

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Ultrafast Self-Assembly of Bottlebrush Statistical Copolymers: Well-Ordered Nanostructures from One-Pot Polymerizations

Cited by 11 publications

References 52 publications

Hierarchical Self-Assembly of ABC-Type Bottlebrush Copolymers

Hierarchical Self-Assembly of ABC-Type Bottlebrush Copolymers

Rapid Access to Diverse Multicomponent Hierarchical Nanostructures from Mixed‐Graft Block Copolymers

Pyrrole-Containing ABA Triblock Brush Polymers as Dual Functional Molecules to Facilely Access Diverse Mesostructured Materials

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