Stimuli-responsive molecular brushes

Lee, Hyung il; Pietrasik, Joanna; Sheiko, Sergei S.; Matyjaszewski, Krzysztof

doi:10.1016/j.progpolymsci.2009.11.002

Cited by 603 publications

(464 citation statements)

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“…Here we provide a general overview of bottlebrush synthesis; more detailed information can be found in review articles by Matyjaszewski and Sheiko et al 14 and by Hu and Huang et al. 15 The synthesis of bottlebrush polymers is achieved with grafting-through, grafting-from, and grafting-to approaches (see Fig.…”

Section: Synthesis Of Bottlebrush Polymersmentioning

confidence: 99%

“…The grafting-from approach is more scalable and versatile in terms of the different types and quantities of bottlebrushes that have been produced 14 . This approach would be optimal for applications involving bulk materials or bottlebrush coatings.…”

Section: Synthesis Of Bottlebrush Polymersmentioning

confidence: 99%

“…The field has also advanced significantly in the understanding of physical properties of bottlebrushes, and work is increasingly focused on bottlebrush assemblies in unique environments rather than the conformation of individual bottlebrushes. Interest in bottlebrush polymers, as measured by literature citations, has grown steadily over the past two decades ( number of very informative reviews, both on bottlebrush synthesis and physical properties [12][13][14] . A tutorial review by Hu and Huang et al discusses advances in the synthesis of graft and bottlebrush polymers 15 .…”

Section: Introductionmentioning

confidence: 99%

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Structure, function, self-assembly, and applications of bottlebrush copolymers

et al. 2015

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Bottlebrush polymers are a type of branched or graft polymer with polymeric side-chains attached to a linear backbone, and the unusual architecture of bottlebrushes provides a number of unique and potentially useful properties. These include a high entanglement molecular weight, enabling rapid self-assembly of bottlebrush block copolymers into large domain structures, the self-assembly of bottlebrush block copolymer micelles in a selective solvent even at very low dilutions, and the functionalization of bottlebrush side-chains for recognition, imaging, or drug 2 delivery in aqueous environments. This review article focuses on recent developments in the field of bottlebrush polymers with an emphasis on applications of bottlebrush copolymers.Bottlebrush copolymers contain two (or more) different types of polymeric side-chains. Recent work has explored the diverse properties and functions of bottlebrush polymers and copolymers in solutions, films, and melts, and applications explored include photonic materials, bottlebrush films for lithographic patterning, drug delivery, and tumor detection and imaging. We provide a brief introduction to bottlebrush synthesis and physical properties and then discuss work related to: i) bottlebrush self-assembly in melts and bulk thin films, ii) bottlebrushes for photonics and lithography, iii) bottlebrushes for small molecule encapsulation and delivery in solution, and iv) bottlebrush micelles and assemblies in solution. We briefly discuss three potential areas for future research, including developing a more quantitative model of bottlebrush self-assembly in the bulk, studying the properties of bottlebrushes at interfaces, and investigating the solution assembly of bottlebrush copolymers.

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Section: Synthesis Of Bottlebrush Polymersmentioning

confidence: 99%

Section: Synthesis Of Bottlebrush Polymersmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Structure, function, self-assembly, and applications of bottlebrush copolymers

et al. 2015

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“…Such polymers are widely termed 2 "cylindrical molecular brushes" due to their steric-induced stiffness and axes of symmetry. [39][40][41][42][43] These cylindrical brushes can be modeled as wormlike chains with the same average crosssectional radius (Rc) along the entire backbone. 5,[44][45][46] On the other hand, if the macromonomer and diluent copolymerize at different rates, the resulting gradient sequences are anticipated to template different side chain conformations.…”

Section: Introductionmentioning

confidence: 99%

Design, Synthesis, and Self-Assembly of Polymers with Tailored Graft Distributions

et al. 2017

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Grafting density and graft distribution impact the chain dimensions and physical properties of polymers. However, achieving precise control over these structural parameters presents long-standing synthetic challenges. In this report, we introduce a versatile strategy to synthesize polymers with tailored architectures via grafting-through ring-opening metathesis polymerization (ROMP). One-pot copolymerization of an ω-norbornenyl macromonomer and a discrete norbornenyl co-monomer (diluent) provides opportunities to control the backbone sequence and therefore the side chain distribution. Toward sequence control, the homopolymerization kinetics of 23 diluents were studied, representing diverse variations in the stereochemistry, anchor groups, and substituents. These modifications tuned the homopolymerization rate constants over two orders of magnitude (0.36 M −1 s −1 < khomo < 82 M −1 s −1 ). Rate trends were identified and elucidated by complementary mechanistic and density functional theory (DFT) studies. Building on this foundation, complex architectures were achieved through copolymerizations of selected diluents with a poly(D,L-lactide) (PLA), polydimethylsiloxane (PDMS), or polystyrene (PS) macromonomer. The cross-propagation rate constants were obtained by non-linear least squares fitting of the instantaneous co-monomer concentrations according to the Mayo-Lewis terminal model. Indepth kinetic analyses indicate a wide range of accessible macromonomer/diluent reactivity ratios (0.08 < r1/r2 < 20), corresponding to blocky, gradient, or random backbone sequences. We further demonstrated the versatility of this copolymerization approach by synthesizing AB graft diblock polymers with tapered, uniform, and inverse-tapered molecular "shapes." Small-angle X-ray scattering analysis of the self-assembled structures illustrates effects of the graft distribution on the domain spacing and backbone conformation. Collectively, the insights provided herein into the ROMP mechanism, monomer design, and homo-and copolymerization rate trends offer a general strategy for the design and synthesis of graft polymers with arbitrary architectures. Controlled copolymerization therefore expands the parameter space for molecular and materials design.

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“…28,29 Compared to radical polymerization of macromonomers, Suzuki coupling polycondensation using AB macromonomers effectively decreases the influence of the concentrations of macromonomers. 2 Suzuki coupling also has the advantage of a mild reaction condition and can be easily controlled compared to other methods such as atom transfer radical polymerization (ATRP), 30 anionic polymerization, 31 and ring-opening polymerization 32 for the preparation of comb polymers. However, polycondensation methods usually give polymers with a broader molecular weight distribution than living radical polymerizations.…”

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confidence: 99%