Solvent-free, supersoft and superelastic bottlebrush melts and networks

Daniel, William F. M.; Burdyńska, Joanna; Vatankhah‐Varnoosfaderani, Mohammad; Matyjaszewski, Krzysztof; Paturej, Jarosław; Rubinstein, Michael; Dobrynin, Andrey V.; Sheiko, Sergei S.

doi:10.1038/nmat4508

Cited by 458 publications

(676 citation statements)

References 28 publications

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“…Previously we have defined side chain length (n sc ), backbone length (n bb ), and grafting density (z). The scaling theory proposed by Rubinstein et al 9 used several variables to define the space filling of the graft polymers. While intuitive, the grafting density does not reflect a chain length.…”

Section: Graft Polymer Variablesmentioning

confidence: 99%

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Consequences of Grafting Density on the Linear Viscoelastic Behavior of Graft Polymers

et al. 2018

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The linear viscoelastic behavior of poly(norbornene)-graft-poly(±-lactide) was investigated as a function of grafting density and overall molar mass. Eight sets of polymers with grafting densities ranging from 0 to 100% were synthesized by living ring-opening metathesis copolymerization. Within each set, the graft chain molar mass and spacing between grafts were fixed, while the total backbone length was varied. Dynamic master curves reveal that these polymers display Rouse and reptation dynamics with a sharp transition in the zero-shear viscosity data, demonstrating that grafting density strongly impacts the entanglement molar mass. The entanglement modulus (G e) scales with inverse grafting density (n g) as G e ∼ n g 1.2 and G e ∼ n g 0 in accordance with scaling theory in the high and low grafting density limits, respectively. However, a sharp transition between these limiting behaviors occurs, which does not conform to existing theoretical models for graft polymers. A molecular interpretation based on thin flexible chains at low grafting density and thick semiflexible chains at high grafting density anticipates the sharp transition between the limiting dynamical regimes.

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Section: Graft Polymer Variablesmentioning

confidence: 99%

“…The coordination number, or the number of side chains that can fit in the pervaded space of one side chain, is very important to the theory proposed by Rubinstein et al 9 Here, we estimate the coordination number, C, according to Eq. S13.…”

Section: Coordination Number Of Side Chainsmentioning

confidence: 99%

Consequences of Grafting Density on the Linear Viscoelastic Behavior of Graft Polymers

et al. 2018

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“…However, the generality of these effects needs to be established with further experiments. First, the JKR-YD crossover should be explored for a wider range of materials including hydrogels and recently-developed monophasic ultrasoft materials [48]. The effect of solid-vapour surface tension should also impact nanoscale contacts on stiffer polymeric materials, like elastomers [49].…”

Section: B Adhesionmentioning

confidence: 99%

Solid capillarity: when and how does surface tension deform soft solids?

et al. 2016

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Soft solids differ from stiff solids in an important way: their surface stresses can drive large deformations. Based on a topical workshop held in the Lorentz Center in Leiden, this Opinion highlights some recent advances in the growing field of solid capillarity and poses key questions for its advancement. Capillarity of Soft InterfacesW o r k s h o p : 2 -6 N o v e m b e r 2 0 1 5 , L e i d e n , t h e N e t h e r l a n d s T h e Lo re nt z Ce nte r is a n i nte r n at i o n a l center in the sciences. Its aim is to organize workshops for scientists in an atm osp h ere that fos ter s co llab o r ati ve work, discussions and interactions. F o r r e g i s t r a t i o n s e e : w w w . l o r e n t z c e n t e r . n lThe forces that hold a water droplet together also pull on delicate objects such as the leaves and petals of plants. Photo CC BY-NC-SA 2.0 by Cé dric Fayemendy. Pos ter design: Sup erNova Studios . NL

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“…The grafting density and distribution of grafts along the backbone determine the steric interactions between side chains and in turn influence the physical properties. Graft polymers display many unique properties compared to their linear analogues, such as extended chain conformations, [5][6][7][8] increased entanglement molecular weights, [9][10][11][12] and architecturedependent rheological behavior. [13][14][15][16] Recent studies have harnessed these properties in a wide variety of applications in photonics, [17][18][19] drug delivery, [20][21][22] transport, [23][24] and thermoplastics.…”

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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Solvent-free, supersoft and superelastic bottlebrush melts and networks

Cited by 458 publications

References 28 publications

Consequences of Grafting Density on the Linear Viscoelastic Behavior of Graft Polymers

Consequences of Grafting Density on the Linear Viscoelastic Behavior of Graft Polymers

Solid capillarity: when and how does surface tension deform soft solids?

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

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