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

Liang, Heyi; Grest, Gary S.; Dobrynin, Andrey V.

doi:10.1021/acsmacrolett.9b00519

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

Full Record
Other Related Research

Abstract

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. In this work, 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. Specifically, we use coarse-grained molecular dynamics simulations to demonstrate that the packing number is a nonmonotonic function of the ratio R_nsc/R_ng of the size of the side chains R_nsc to that of the backbone spacer between neighboring grafting points R_ng. This parameter characterizes the degree of mutual interpenetration between side chains of the same macromolecule. We demonstrate that P_e of brush-like polymers first decreases with increasing side chain grafting density in the dilute side chain regime (R_nsc < R_ng), then begins to increase in the regime of overlapping side chains (R_nsc > R_ng), approaching the value for linear chains in the limit of densely grafted side chains. This dependence ofmore »« less

Authors:

^[1];

^[2];

^[1]

Univ. of Akron, OH (United States)
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Publication Date:: Thu Sep 26 00:00:00 EDT 2019

Research Org.:: Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Sponsoring Org.:: USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF)

OSTI Identifier:: 1574445

Report Number(s):: SAND-2019-12126J
Journal ID: ISSN 2161-1653; 680158

Grant/Contract Number:: AC04-94AL85000; NA-0003525

Resource Type:: Accepted Manuscript

Journal Name:: ACS Macro Letters

Additional Journal Information:: Journal Volume: 8; Journal Issue: 10; Journal ID: ISSN 2161-1653

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE

Citation Formats


                    Liang, Heyi, Grest, Gary S., and Dobrynin, Andrey V. Brush-Like Polymers and Entanglements: From Linear Chains to Filaments.  United States: N. p., 2019. 
Web.  doi:10.1021/acsmacrolett.9b00519.

Copy to clipboard


                    Liang, Heyi, Grest, Gary S., & Dobrynin, Andrey V. Brush-Like Polymers and Entanglements: From Linear Chains to Filaments.  United States.  https://doi.org/10.1021/acsmacrolett.9b00519

Copy to clipboard


                    Liang, Heyi, Grest, Gary S., and Dobrynin, Andrey V. Thu .  
"Brush-Like Polymers and Entanglements: From Linear Chains to Filaments".  United States.  https://doi.org/10.1021/acsmacrolett.9b00519.  https://www.osti.gov/servlets/purl/1574445.

Copy to clipboard


                    
@article{osti_1574445,

  title        = {Brush-Like Polymers and Entanglements: From Linear Chains to Filaments},

  author       = {Liang, Heyi and Grest, Gary S. and Dobrynin, Andrey V.},

  abstractNote = {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 Pe, the number of polymer strands within a confining tube that is required for chains to entangle. In this work, we show that in melts of brush-like (graft) polymers, consisting of linear chain backbones with grafted side chains, Pe is not a universal number and depends on the molecular architecture. Specifically, we use coarse-grained molecular dynamics simulations to demonstrate that the packing number is a nonmonotonic function of the ratio Rnsc/Rng of the size of the side chains Rnsc to that of the backbone spacer between neighboring grafting points Rng. This parameter characterizes the degree of mutual interpenetration between side chains of the same macromolecule. We demonstrate that Pe of brush-like polymers first decreases with increasing side chain grafting density in the dilute side chain regime (Rnsc < Rng), then begins to increase in the regime of overlapping side chains (Rnsc > Rng), 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.},

  doi          = {10.1021/acsmacrolett.9b00519},

  journal      = {ACS Macro Letters},

  number       = 10,

  volume       = 8,

  place        = {United States},

  year         = {Thu Sep 26 00:00:00 EDT 2019},

  month        = {Thu Sep 26 00:00:00 EDT 2019}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/acsmacrolett.9b00519

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 8 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

Fluorinated bottlebrush polymers based on poly(trifluoroethyl methacrylate): Synthesis and characterizations

Journal Article Xu, Yuewen ; Wang, Weiyu ; Wang, Yangyang ; ... - Polymer Chemistry

Bottlebrush polymers are densely grafted polymers with long side-chains attached to a linear polymeric backbone. Their unusual structures endow them with a number of unique and potentially useful properties in solution, in thin films, and in bulk. Despite the many studies of bottlebrushes that have been reported, the structure–property relationships for this class of materials are still poorly understood. In this contribution, we report the synthesis and characterization of fluorinated bottlebrush polymers based on poly(2,2,2-trifluoroethyl methacrylate). The synthesis was achieved by atom transfer radical polymerization (ATRP) using an α-bromoisobutyryl bromide functionalized norbornene initiator, followed by ring-opening metathesis polymerization (ROMP) usingmore »« less
Cited by 34
https://doi.org/10.1039/C5PY01514F

Full Text Available
Nanoporous poly(3-hexylthiophene) thin film structures from self-organization of a tunable molecular bottlebrush scaffold

Journal Article Ahn, Suk-kyun ; Carrillo, Jan-Michael Y. ; Keum, Jong K. ; ... - Nanoscale

The ability to widely tune the design of macromolecular bottlebrushes provides access to self-assembled nanostructures formed by microphase segregation in melt, thin film and solution that depart from structures adopted by simple linear copolymers. A series of random bottlebrush copolymers containing poly(3-hexylthiophene) (P3HT) and poly(D,L-lactide) (PLA) side chains grafted on a poly(norbornene) backbone were synthesized via ring-opening metathesis polymerization (ROMP) using the grafting through approach. P3HT side chains induce a physical aggregation of the bottlebrush copolymers upon solvent removal by vacuum drying, primarily driven by attractive π–π interactions; however, the amount of aggregation can be controlled by adjusting side chainmore »« less
Cited by 17
https://doi.org/10.1039/C7NR00015D

Full Text Available
Hydrogen-Bonding Bottlebrush Networks: Self-Healing Materials from Super-Soft to Stiff

Journal Article Xie, Renxuan ; Lapkriengkri, Intanon ; Pramanik, Nabendu B. ; ... - Macromolecules

The impact of polymer architecture on network dynamics and self-healing is presented using bottlebrushes containing side chains that are end-functionalized with 2-ureido-4[1H]-pyrimidinone (UPy). The synthesis of these materials is straightforward through a three-step process: (1) synthesizing rubbery poly(4-methylcaprolactone) macromonomers (p4MCL–OH) with a norbornene-based initiator, (2) functionalizing the terminal hydroxyl group with UPy–isocyanate (p4MCL–UPy), and (3) statistically copolymerizing p4MCL–OH and p4MCL–UPy via ring-opening metathesis polymerization (ROMP) to form hydrogen-bonding bottlebrushes having a fraction (p) of side chains functionalized with UPy. Attaching UPy to the free end of bottlebrush side chains dilutes the impact of friction from complementary UPy interactions on segmentalmore »« less
https://doi.org/10.1021/acs.macromol.2c01886

Full Text Available
Development and Modeling of a Novel Self-Assembly Process for Polymer and Polymeric Composite Nanoparticles

Book Sumpter, Bobby G. ; Carrillo, Jan-Michael Y. ; Ahn, Suk-Kyun ; ...

Extensive computational simulations and experiments have been used to investigate the structure, dynamics and resulting photophysical properties of a number para-phenylenevinylene (PPV) based polymers and oligomers. These studies have shown how the morphology and structure are controlled to a large extent by the nature of the solute-solvent interactions in the initial solution phase preparation. A good solvent such as dichloromethane generates non-compact structures with more of a defect-extended chain like morphology while a bad solvent such as toluene leads to compact organized and folded structures with rod-like morphologies. Secondary structural organization is induced by using the solution phase structures tomore »« less
https://doi.org/10.1201/9781315374581-9
Design, Synthesis, and Self-Assembly of Polymers with Tailored Graft Distributions

Journal Article Chang, Alice B. ; Lin, Tzu-Pin ; Thompson, Niklas B. ; ... - Journal of the American Chemical Society

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 overmore »« less
Cited by 90
https://doi.org/10.1021/jacs.7b10525

Full Text Available

Similar Records