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Bottlebrush polymers, macromolecules consisting of dense polymer side chains grafted from a central polymer backbone, have unique properties resulting from this well-defined molecular architecture. With the advent of controlled radical polymerization techniques, access to these architectures has become more readily available. However, synthetic challenges remain, including the need for intermediate purification, the use of toxic solvents, and challenges with achieving long bottlebrush architectures due to backbone entanglements. Herein, we report hybrid bonding bottlebrush polymers (systems integrating covalent and noncovalent bonding of structural units) consisting of poly(sodium 4-styrenesulfonate) (p(NaSS)) brushes grafted from a peptide amphiphile (PA) supramolecular polymer backbone. This was achieved using photoinitiated electron/energy transfer-reversible addition–fragmentation chain transfer (PET-RAFT) polymerization in water. The structure of the hybrid bonding bottlebrush architecture was characterized using cryogenic transmission electron microscopy, and its properties were probed using rheological measurements. We observed that hybrid bonding bottlebrush polymers were able to organize into block architectures containing domains with high brush grafting density and others with no observable brushes. This finding is possibly a result of dynamic behavior unique to supramolecular polymer backbones, enabling molecular exchange or translational diffusion of monomers along the length of the assemblies. The hybrid bottlebrush polymers exhibited higher solution viscosity at moderate shear, protected supramolecular polymer backbones from disassembly at high shear, and supported self-healing capabilities, depending on grafting densities. Our results demonstrate an opportunity for novel properties in easily synthesized bottlebrush polymer architectures built with supramolecular polymers that might be useful in biomedical applications or for aqueous lubrication.
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From Fully Stretched to Collapsed Chains: Bottlebrush Polymer Grafted Particles
Macromolecular architecture is a critical parameter when tuning polymer material properties. Although the implementation of non-linear polymers in different applications has grown over the years, polymer grafted surfaces such as nanoparticles have traditionally been composed of linear thermoplastic polymers, with a limited number of examples demonstrating a diversity in polymer architectures. In an effort to combine polymer architecturally dependent material properties with polymer grafted particles (PGPs), as opposed to conventional methods of tuning polymer grafting parameters such as the number of chains per surface area (i.e., polymer graft density), a series of bottlebrush grafted particles were synthesized using surface-initiated ring-opening metathesis polymerization (SI-ROMP). These bottlebrush PGPs are composed of glassy, semi-crystalline, and elastomeric polymer side chains with controlled backbone degrees of polymerization (Nbb) at relatively constant polymer graft density on the surface of silica particles with diameters equaling approximately 160 or 77 nm. Bottlebrush polymer chain conformations, evaluated by measuring the brush height of surface grafted polymer chains in solution and the melt, undergo drastic changes in macromolecular dimensions in different environments. In solution, brush heights increase linearly as a function of Nbb, consistent with fully stretched chains, which is confirmed using cryogenic transmission electron microscopy (Cryo-TEM). Meanwhile, brush heights are consistently at a minimum in the melt, indicative of chains collapsed on the particle surface. The conformational extremes for grafted bottlebrush polymers are unseen in any linear polymer chain systems, highlighting the effect of macromolecular architecture and surface grafting. Bottlebrush grafted particles are an exciting class of materials where diversifying polymer architectures will expand PGP material design rules that harness macromolecular architecture to dictate properties.
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- Award ID(s):
- 1942508
- PAR ID:
- 10594463
- Publisher / Repository:
- ACS
- Date Published:
- Journal Name:
- Macromolecules
- Volume:
- 57
- Issue:
- 20
- ISSN:
- 0024-9297
- Page Range / eLocation ID:
- 9616 to 9626
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Although the behavior of single chains is integral to the foundation of polymer science, a clear and convincing image of single chains in the solid state has still not been captured. For bottlebrush polymers, understanding their conformation in bulk materials is especially important because their extended backbones may explain their self-assembly and mechanical properties that have been attractive for many applications. Here, single-bottlebrush chains are visualized using single-molecule localization microscopy to study their conformations in a polymer melt composed of linear polymers. By observing bottlebrush polymers with different side chain lengths and grafting densities, we observe the relationship between molecular architecture and conformation. We show that bottlebrushes are significantly more rigid in the solid state than previously measured in solution, and the scaling relationships between persistence length and side chain length deviate from those predicted by theory and simulation. We discuss these discrepancies using mechanisms inspired by polymer-grafted nanoparticles, a conceptually similar system. Our work provides a platform for visualizing single-polymer chains in an environment made up entirely of other polymers, which could answer a number of open questions in polymer science.more » « less
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Grafting polymers to nanoparticle surfaces influences properties from the conformation of the polymer chains to the dispersion and assembly of nanoparticles within a polymeric material. Recently, a small body of work has begun to address the question of how grafting polymers to a nanoparticle surface impacts chain dynamics, and the resulting physical properties of a material. This Review discusses recent work that characterizes the structure and dynamics of polymers that are grafted to nanoparticles and opportunities for future research. Starting from the case of a single polymer chain attached to a nanoparticle core, this Review follows the structure of the chains as grafting density increases, and how this structure slows relaxation of polymer chains and affects macroscopic material properties.more » « less
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null (Ed.)Polyethylene oxide (PEO)-based polymers are commonly studied for use as a solid polymer electrolyte for rechargeable Li-ion batteries; however, simultaneously achieving sufficient mechanical integrity and ionic conductivity has been a challenge. To address this problem, a customized polymer architecture is demonstrated wherein PEO bottle-brush arms are hyperbranched into a star architecture and then functionalized with end-grafted, linear PEO chains. The hierarchical architecture is designed to minimize crystallinity and therefore enhance ion transport via hyperbranching, while simultaneously addressing the need for mechanical integrity via the grafting of long, PEO chains ( M n = 10,000). The polymers are doped with lithium bis(trifluoromethane) sulfonimide (LiTFSI), creating hierarchically hyperbranched (HB) solid polymer electrolytes. Compared to electrolytes prepared with linear PEO of equivalent molecular weight, the HB PEO electrolytes increase the room temperature ionic conductivity from ∼2.5 × 10 –6 to 2.5 × 10 −5 S/cm. The conductivity increases by an additional 50% by increasing the block length of the linear PEO in the bottle brush arms from M n = 1,000 to 2,000. The mechanical properties are improved by end-grafting linear PEO ( M n = 10,000) onto the terminal groups of the HB PEO bottle-brush. Specifically, the Young’s modulus increases by two orders of magnitude to a level comparable to commercial PEO films, while only reducing the conductivity by 50% below the HB electrolyte without grafted PEO. This study addresses the trade-off between ion conductivity and mechanical properties, and shows that while significant improvements can be made to the mechanical properties with hierarchical grafting of long, linear chains, only modest gains are made in the room temperature conductivity.more » « less
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We present a novel type of magnetorheological material that allows one to restructure the magnetic particles inside the finished composite, tuning in situ the viscoelasticity and magnetic response of the material in a wide range using temperature and an applied magnetic field. The polymer medium is an A-g-B bottlebrush graft copolymer with side chains of two types: polydimethylsiloxane and polystyrene. At room temperature, the brush-like architecture provides the tissue mimetic softness and strain stiffening of the elastomeric matrix, which is formed through the aggregation of polystyrene side chains into aggregates that play the role of physical cross-links. The aggregates partially dissociate and the matrix softens at elevated temperatures, allowing for the effective rearrangement of magnetic particles by applying a magnetic field in the desired direction. Magnetoactive thermoplastic elastomers (MATEs) based on A-g-B bottlebrush graft copolymers with different amounts of aggregating side chains filled with different amounts of carbonyl iron microparticles were prepared. The in situ restructuring of magnetic particles in MATEs was shown to significantly alter their viscoelasticity and magnetic response. In particular, the induced anisotropy led to an order-of-magnitude enhancement of the magnetorheological properties of the composites.more » « less
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acs.macromol.4c00881
