Molecular Bottlebrushes Featuring Brush-on-Brush Architecture

Chen, Yi; Sun, Ziyang; Li, Huaan; Dai, Yunkai; Hu, Zhitao; Huang, Hui; Shi, Yi; Li, Yuanchao; Chen, Yongming

doi:10.1021/acsmacrolett.9b00399

Cited by 34 publications

(24 citation statements)

References 43 publications

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“…The simulation results are in a qualitative agreement with similar dependence of the packing number obtained from plateau shear modulus in melts of graft poly(n-butyl acrylates) (PBA) and poly(norbornene)-graf t-poly(lactide) (PNB-g-PLA; Figure 3b). 25,26 Our results could play an important role in understanding viscoelastic properties of solutions and melts of complex graft polymers in which side chains have brush-like 36 and dendrimer-like 37−39 structures.…”

Section: Acs Macro Lettersmentioning

confidence: 82%

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Brush-Like Polymers and Entanglements: From Linear Chains to Filaments

2019

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Dynamics of melts and solutions of high molecular weight polymers and biopolymers is controlled by topological constraints (entanglements) imposing a sliding chain motion along an effective confining tube. For linear chains, the tube size is determined by universal packing number P e, the number of polymer strands within a confining tube that is required for chains to entangle. Here we show that in melts of brush-like (graft) polymers, consisting of linear chain backbones with grafted side chains, P e is not a universal number and depends on the molecular architecture. In particular, we use coarse-grained molecular dynamics simulations to demonstrate that the packing number is a nonmonotonic function of the ratio R n sc /R n g of the size of the side chains R n sc to that of the backbone spacer between neighboring grafting points R n g . This parameter characterizes the degree of mutual interpenetration between side chains of the same macromolecule. We show that P e of brush-like polymers first decreases with increasing side chain grafting density in the dilute side chain regime (R n sc < R n g ), then begins to increase in the regime of overlapping side chains (R n sc > R n g ), approaching the value for linear chains in the limit of densely grafted side chains. This dependence of the packing number reflects a crossover from chain-like entanglements in systems with loosely grafted side chains (comb-like polymers) to entanglements between flexible filaments (bottlebrush-like polymers). Our simulation results are in agreement with the experimental data for the dependence of a plateau modulus on the molecular architecture of graft poly(n-butyl acrylates) and poly(norbornene)-graft-poly(lactide) melts.

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Section: Acs Macro Lettersmentioning

confidence: 82%

“…Our results could play an important role in understanding viscoelastic properties of solutions and melts of complex graft polymers in which side chains have brush-like and dendrimer-like − structures.…”

mentioning

confidence: 82%

Brush-Like Polymers and Entanglements: From Linear Chains to Filaments

2019

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“…This is because longer chains have a larger coil size in solution and therefore it is more difficult for them to react with other polymer chains. 31 AFM was then used to further visualize the morphology of the resulting PAMA 147 -g-PDMA x bottlebrush polymers. Polymer samples were prepared by spin-casting the dilute aqueous solution onto the freshly cleaved mica surface.…”

Section: Papermentioning

confidence: 99%

An efficient O-phthalaldehyde-amine coupling reaction for the synthesis of a bottlebrush polymer under physiological conditions

et al. 2022

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“…Especially, copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction (“click” reaction) has provided an extremely powerful tool and been widely used in this synthesis approach due to its good tolerance of functionality, moderate reaction conditions, high yields, and simple purification procedures . Through the combination of multiple methods, molecular bottlebrushes of various morphologies have been prepared, including Janus-type well-defined asymmetric molecular double-brushes, , molecular stars with bottlebrush arms, − brush-on-brush molecular bottlebrushes, , molecular bottlebrushes with linear polymer tails, , bottlebrush block copolymers, − molecular bottlebrushes with dendritic or cyclic side chains, and molecular bottlebrushes with multiple side chains per repeating backbone unit …”

Section: Introductionmentioning

confidence: 99%

Core–Shell Copolymers with Brush-on-Hyperbranched Arm Architecture: Synthesis, Dual Thermoresponsive Behaviors, and Nanocarriers

et al. 2021

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A series of core−shell copolymers with brush-on-hyperbranched arm architecture were synthesized and characterized in detail. These copolymers were prepared via the combination of cationic ring-opening polymerization (CROP) and azide-alkyne "click" chemistry. The primary hyperbranched polyether core (HPEHO) was synthesized via the CROP of 3-ethyl-3-(hydroxymethyl)oxetane (EHO). Subsequently, the outer layer of glycidyl azide polymer (GAP) linear arms was prepared through the CROP of epichlorohydrin (ECH), followed by azidation of the chlorine atoms. Poly(ethylene glycol) (PEG) was last grafted onto the GAP chains via "click" reaction to obtain an amphiphilic core−shell structure. These core−shell copolymers exhibited a lower critical solution temperature (LCST)-type behavior in aqueous solutions. The LCST cloud point (CP) temperature not only decreased with an increasing polymer concentration but also was dependent on the molecular architecture that it increased upon increasing the PEG brush lengths and GAP arm lengths. More interestingly, while the free PEG chains were completely soluble in THF, an upper critical solution temperature (UCST) transition was observed for these core−shell copolymers in THF, and the CP shifted toward higher temperatures with increasing GAP linear arm lengths and concentrations. Last, the PEG outer shell and hydrophobic interior polyether core made these copolymers decent nanocarriers for hydrophobic cargo molecules in aqueous solutions.

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Molecular Bottlebrushes Featuring Brush-on-Brush Architecture

Cited by 34 publications

References 43 publications

Brush-Like Polymers and Entanglements: From Linear Chains to Filaments

Brush-Like Polymers and Entanglements: From Linear Chains to Filaments

An efficient O-phthalaldehyde-amine coupling reaction for the synthesis of a bottlebrush polymer under physiological conditions

Core–Shell Copolymers with Brush-on-Hyperbranched Arm Architecture: Synthesis, Dual Thermoresponsive Behaviors, and Nanocarriers

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