Efficient Synthesis of Narrowly Dispersed Brush Polymers via Living Ring-Opening Metathesis Polymerization of Macromonomers

Xia, Yan; Kornfield, Julia A.; Grubbs, Robert H.

doi:10.1021/ma900280c

Cited by 299 publications

(395 citation statements)

References 54 publications

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“…Ring opening metathesis polymerization (ROMP) of norbornenyl macromonomers has been shown to be an effective grafting-through synthesis strategy, such as the example shown in Fig. 3B 22 .…”

Section: Synthesis Of Bottlebrush Polymersmentioning

confidence: 99%

“…Subsequently, in 2008, Xia and Grubbs et al reported the use of a highly-active ruthenium catalyst for achieving improved control over bottlebrush molecular weight and molecular weight dispersity 22,33 . The reactivity of norbornenyl macromonomers in ROMP is sufficient for achieving high macromonomer conversions for a range of concentrations and macromonomer molecular weights, enabling the preparation of bottlebrush polymers with systematically varying backbone and side-chain lengths.…”

Section: Synthesis Of Bottlebrush Polymersmentioning

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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“…Ring opening metathesis polymerization (ROMP) of norbornenyl macromonomers has been shown to be an effective grafting-through synthesis strategy, such as the example shown in Fig. 3B 22 .…”

Section: Synthesis Of Bottlebrush Polymersmentioning

confidence: 99%

Section: Synthesis Of Bottlebrush Polymersmentioning

confidence: 99%

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

et al. 2015

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“…(H 2 IMes)(pyr) 2 (Cl) 2 RuCHPh 1 , N-(hydroxyethyl)-cis-5-norbornene-exo-2,3-dicarboximide 2 , and N-(pentynoyl decanyl)-cis-5-norbornene-exo-2,3-dicarboximide 3 were prepared as described previously. The synthesis and characterization of PMA, PtBA, and PS MMs have been reported previously 3 and the PnBA MM was synthesized in a similar manner. n-BA was passed through a column of basic alumina immediately before use.…”

Section: Methodsmentioning

confidence: 99%

Efficient Synthesis of Narrowly Dispersed Brush Copolymers and Study of Their Assemblies: The Importance of Side Chain Arrangement

et al. 2009

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Efficient, one-pot preparation of synthetically challenging, high molecular weight (MW), narrowly dispersed brush block copolymers and random copolymers in high conversions was achieved by ring-opening metathesis (co)polymerization (ROMP) of various macromonomers (MMs) using the highly active, fast-initiating ruthenium olefin metathesis catalyst (H2IMes)(pyr)2(Cl)2RuCHPh. A series of random and block copolymers were prepared from a pair of MMs containing polylactide (PLA) and poly(n-butyl acrylate) (PnBA) side chains at similar MWs. Their self-assembly in the melt state was studied by small-angle X-ray scattering (SAXS) and atomic force microscopy (AFM). In brush random copolymers containing approximately equal volume fractions of PLA and PnBA, the side chains segregate into lamellae with domain spacing of 14 nm as measured by SAXS, which was in good agreement with the lamellar thickness measured by AFM. The domain spacings and order−disorder transition temperatures of brush random copolymers were insensitive to the backbone length. In contrast, brush block copolymers containing approximately equal volume fractions of these MMs self-assembled into highly ordered lamellae with domain spacing over 100 nm. Their assemblies suggested that the brush block copolymer backbone adopted an extended conformation in the ordered state.

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“…The x-I anchor group has been widely incorporated in macromonomers toward the synthesis of bottlebrush polymers by grafting-through ROMP, 21,55,[57][58][59] motivating our interest in imide-based diluents. Compared to diester anchor groups, imides are more rigid due 4 to their fused rings and thereby change the monomer steric profile.…”

Section: Chart 1 Monomer Design For Ring-opening Metathesis Copolymementioning

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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Efficient Synthesis of Narrowly Dispersed Brush Polymers via Living Ring-Opening Metathesis Polymerization of Macromonomers

Cited by 299 publications

References 54 publications

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

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

Efficient Synthesis of Narrowly Dispersed Brush Copolymers and Study of Their Assemblies: The Importance of Side Chain Arrangement

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

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