Rapid self-assembly of brush block copolymers to photonic crystals

Sveinbjörnsson, Benjamín R.; Weitekamp, Raymond A.; Miyake, Garret M.; Xia, Yan; Atwater, Harry A.; Grubbs, Robert H.

doi:10.1073/pnas.1213055109

Cited by 353 publications

(399 citation statements)

References 34 publications

Supporting

Mentioning

379

Contrasting

Unclassified

Order By: Relevance

“…Grubbs et al studied the photonic properties of a series of PS/PLA bottlebrush block copolymer to understand the role of molecular weight and processing conditions on domain size 112 These assembled rapidly on solvent casting and exhibited a tuneable selective reflection band over a broad range of wavelengths 115 .…”

Section: Bulk and Thin Film Applications Of Bottlebrush Copolymersmentioning

confidence: 99%

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

et al. 2015

View full text Add to dashboard Cite

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.

show abstract

Section: Bulk and Thin Film Applications Of Bottlebrush Copolymersmentioning

confidence: 99%

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

et al. 2015

View full text Add to dashboard Cite

show abstract

“…[49][50][51][52] We targeted poly(D,L-lactide)-b-polystyrene (PLA-b-PS) graft diblock polymers to permit comparisons with brush PLA-b-PS systems previously investigated in the context of self-assembly. [21][22][23][24][25] All polymerizations were carried out in CH2Cl2 at room temperature under an inert atmosphere. To vary the grafting density (Figure 1), the first block was synthesized by copolymerizing a PLA macromonomer (Mn = 3230 g/mol) with a discrete co-monomer (i.e., diluent), DME (endo,exonorbornenyl dimethyl ester, Mn = 210 g/mol).…”

Section: Resultsmentioning

confidence: 99%

“…We envisage that the determined scaling relationships for various grafting density series could be exploited to guide material design. 63 and PLA 23 were prepared according to previously reported precedures. Norbornene diluents DME 64 and DBE 65 were prepared by Diels-Alder reactions according to previously reported procedures.…”

Section: Discussionmentioning

confidence: 99%

See 1 more Smart Citation

Effects of Grafting Density on Block Polymer Self-Assembly: From Linear to Bottlebrush

et al. 2017

Self Cite

View full text Add to dashboard Cite

Grafting density is an important structural parameter that exerts significant influences over the physical properties of architecturally complex polymers. In this report, the physical consequences of varying the grafting density (z) were studied in the context of block polymer self-assembly. Well-defined block polymers spanning the linear, comb, and bottlebrush regimes (0 ≤ z ≤ 1) were prepared via grafting-through ring-opening-metathesis polymerization. ω-Norbornenyl poly(d,l-lactide) and polystyrene macromonomers were copolymerized with discrete comonomers in different feed ratios, enabling precise control over both the grafting density and molecular weight. Small-angle X-ray scattering experiments demonstrate that these graft block polymers self-assemble into long-range-ordered lamellar structures. For 17 series of block polymers with variable z, the scaling of the lamellar period with the total backbone degree of polymerization (d* ∼ N bb α) was studied. The scaling exponent α monotonically decreases with decreasing z and exhibits an apparent transition at z ≈ 0.2, suggesting significant changes in the chain conformations. Comparison of two block polymer systems, one that is strongly segregated for all z (System I) and one that experiences weak segregation at low z (System II), indicates that the observed trends are primarily caused by the polymer architectures, not segregation effects. A model is proposed in which the characteristic ratio (C ∞), a proxy for the backbone stiffness, scales with N bb as a function of the grafting density: C ∞ ∼ N bb f(z). The scaling behavior disclosed herein provides valuable insights into conformational changes with grafting density, thus introducing opportunities for block polymer and material design.

show abstract

“…Basic methods of these modeling techniques and code can be found in reference (1). In short, the amount of disorder was simulated by varying the domain spacing of the layers within a film by a given coefficient of variation as a means of simulating imperfect films.…”

Section: Modeled Uv-vis Datamentioning

confidence: 99%

Improving Brush Polymer Infrared One-Dimensional Photonic Crystals via Linear Polymer Additives

Macfarlane¹,

et al. 2014

Self Cite

View full text Add to dashboard Cite

Materials:Unless otherwise noted, all solvents and reagents were purchased from VWR or Sigma-Aldrich.The ruthenium-based metathesis catalyst was obtained from Materia Inc. and stored in a drybox prior to use, and the RuO4 SEM staining agent was obtained from Polysciences, Inc and stored at 4 ºC. The ruthenium metathesis catalyst ((H2IMes)(pyr)2(Cl)2RuCHPh) and PLA macromonomer initiator (N-(hydroxyethanyl)-cis-5-norbornene-exo-2,3-dicarboximide) were prepared as described previously (1). Dry solvents were purified by passing them through solvent purification columns, and 3,6-dimethyl-1,4-dioxane-2,5-dione was purified by sublimation under vacuum. All other solvents and chemicals were used without further purification unless otherwise noted. General Information:NMR spectra were recorded at room temperature on a Varian Inova 500 (at 500 MHz), and analyzed on MestReNova software. Gel permeation chromatography (GPC) was carried out in THF on two Plgel 10 μm mixed-B LS columns (Polymer Laboratories) connected in series with a miniDAWN TREOS multiangle laser light scattering (MALLS) detector, a ViscoStar viscometer and Optilab rex differential refractometer (all from Wyatt Technology). The dn/dc values used for the polylactide and polystyrene macromonomers were 0.050 and 0.180 respectively, and dn/dc values for the brush polymers and random copolymers were obtained for each injection by assuming 100% mass elution from the columns. SEM images were taken on a ZEISS 1550 VP

show abstract

Rapid self-assembly of brush block copolymers to photonic crystals

Cited by 353 publications

References 34 publications

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

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

Effects of Grafting Density on Block Polymer Self-Assembly: From Linear to Bottlebrush

Improving Brush Polymer Infrared One-Dimensional Photonic Crystals via Linear Polymer Additives

Contact Info

Product

Resources

About