Conformational Entropy as a Means to Control the Behavior of Poly(diketoenamine) Vitrimers In and Out of Equilibrium

doi:10.1002/ange.201912223

Title: Conformational Entropy as a Means to Control the Behavior of Poly(diketoenamine) Vitrimers In and Out of Equilibrium

Authors:

He, Changfei ^[1]; Christensen, Peter R. ^[2]; Seguin, Trevor J. ^[3]; Dailing, Eric A. ^[2]; Wood, Brandon M. ^[4]; Walde, Rebecca K. ^[2]; Persson, Kristin A. ^[5]; Russell, Thomas P. ^[6];

^[7]

Beijing Advanced Innovation Center, for Soft Matter Science and Engineering Beijing University, of Chemical Technology Beijing 100029 China
The Molecular FoundryLawrence Berkeley National Laboratory 1 Cyclotron Road Berkeley CA 94720 USA
Energy Technologies AreaLawrence Berkeley National Laboratory 1 Cyclotron Road Berkeley CA 94720 USA
Graduate Group of Applied Science and TechnologyUniversity of California Berkeley CA 94720 USA, Environmental Energy Technologies DivisionLawrence Berkeley National Laboratory 1 Cyclotron Road Berkeley CA 94720 USA
Materials Science and Engineering DepartmentUniversity of California Berkeley CA 94720 USA
Beijing Advanced Innovation Center, for Soft Matter Science and Engineering Beijing University, of Chemical Technology Beijing 100029 China, Materials Sciences DivisionLawrence Berkeley National Laboratory 1 Cyclotron Road Berkeley CA 94720 USA, Polymer Science and Engineering DepartmentUniversity of Massachusetts Amherst MA 01003 USA
The Molecular FoundryLawrence Berkeley National Laboratory 1 Cyclotron Road Berkeley CA 94720 USA, Materials Sciences DivisionLawrence Berkeley National Laboratory 1 Cyclotron Road Berkeley CA 94720 USA

Publication Date:: 2019-11-21

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS)

OSTI Identifier:: 1575100

Grant/Contract Number:: AC02-05CH11231

Resource Type:: Publisher's Accepted Manuscript

Journal Name:: Angewandte Chemie

Additional Journal Information:: Journal Name: Angewandte Chemie Journal Volume: 132 Journal Issue: 2; Journal ID: ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)

Country of Publication:: Germany

Language:: English

Citation Formats


                    He, Changfei, Christensen, Peter R., Seguin, Trevor J., Dailing, Eric A., Wood, Brandon M., Walde, Rebecca K., Persson, Kristin A., Russell, Thomas P., and Helms, Brett A. Conformational Entropy as a Means to Control the Behavior of Poly(diketoenamine) Vitrimers In and Out of Equilibrium.  Germany: N. p., 2019. 
        Web.  doi:10.1002/ange.201912223.

Copy to clipboard


                    He, Changfei, Christensen, Peter R., Seguin, Trevor J., Dailing, Eric A., Wood, Brandon M., Walde, Rebecca K., Persson, Kristin A., Russell, Thomas P., & Helms, Brett A. Conformational Entropy as a Means to Control the Behavior of Poly(diketoenamine) Vitrimers In and Out of Equilibrium.  Germany.  doi:10.1002/ange.201912223.

Copy to clipboard


                    He, Changfei, Christensen, Peter R., Seguin, Trevor J., Dailing, Eric A., Wood, Brandon M., Walde, Rebecca K., Persson, Kristin A., Russell, Thomas P., and Helms, Brett A. Thu .  
        "Conformational Entropy as a Means to Control the Behavior of Poly(diketoenamine) Vitrimers In and Out of Equilibrium".  Germany.  doi:10.1002/ange.201912223.

Copy to clipboard


                    
@article{osti_1575100,

  title        = {Conformational Entropy as a Means to Control the Behavior of Poly(diketoenamine) Vitrimers In and Out of Equilibrium},

  author       = {He, Changfei and Christensen, Peter R. and Seguin, Trevor J. and Dailing, Eric A. and Wood, Brandon M. and Walde, Rebecca K. and Persson, Kristin A. and Russell, Thomas P. and Helms, Brett A.},

  abstractNote = {},

  doi          = {10.1002/ange.201912223},

  journal      = {Angewandte Chemie},

  number       = 2,

  volume       = 132,

  place        = {Germany},

  year         = {2019},

  month        = {11}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (Publisher)

Publisher's Version of Record
DOI: 10.1002/ange.201912223

Other availability

Search WorldCat to find libraries that may hold this journal

Save / Share:

Export Metadata

Save to My Library

Works referenced in this record:

Catalyst-Free Thermoset Polyurethane with Permanent Shape Reconfigurability and Highly Tunable Triple-Shape Memory Performance
journal, March 2017

Zheng, Ning; Hou, Jingjing; Xu, Yang
ACS Macro Letters, Vol. 6, Issue 4
DOI: 10.1021/acsmacrolett.7b00037

A Catalyst-Free Epoxy Vitrimer System Based on Multifunctional Hyperbranched Polymer
journal, August 2018

Han, Jiarui; Liu, Tuan; Hao, Cheng
Macromolecules, Vol. 51, Issue 17
DOI: 10.1021/acs.macromol.8b01424

Recyclable, Strong, and Highly Malleable Thermosets Based on Boroxine Networks
journal, May 2018

Ogden, William A.; Guan, Zhibin
Journal of the American Chemical Society, Vol. 140, Issue 20
DOI: 10.1021/jacs.8b03257

Approaches to Sustainable and Continually Recyclable Cross-Linked Polymers
journal, August 2018

Fortman, David J.; Brutman, Jacob P.; De Hoe, Guilhem X.
ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 9
DOI: 10.1021/acssuschemeng.8b02355

Metal-Catalyzed Transesterification for Healing and Assembling of Thermosets
journal, April 2012

Capelot, Mathieu; Montarnal, Damien; Tournilhac, François
Journal of the American Chemical Society, Vol. 134, Issue 18
DOI: 10.1021/ja302894k

DNA-Based Nanodevices Controlled by Purely Entropic Linker Domains
journal, October 2018

Mariottini, Davide; Idili, Andrea; Nijenhuis, Minke A. D.
Journal of the American Chemical Society, Vol. 140, Issue 44
DOI: 10.1021/jacs.8b07640

Silica-Like Malleable Materials from Permanent Organic Networks
journal, November 2011

Montarnal, D.; Capelot, M.; Tournilhac, F.
Science, Vol. 334, Issue 6058
DOI: 10.1126/science.1212648

Thermoset Shape-Memory Polyurethane with Intrinsic Plasticity Enabled by Transcarbamoylation
journal, June 2016

Zheng, Ning; Fang, Zizheng; Zou, Weike
Angewandte Chemie, Vol. 128, Issue 38
DOI: 10.1002/ange.201602847

Chemical control of the viscoelastic properties of vinylogous urethane vitrimers
journal, March 2017

Denissen, Wim; Droesbeke, Martijn; Nicolaÿ, Renaud
Nature Communications, Vol. 8, Issue 1
DOI: 10.1038/ncomms14857

High-performance vitrimers from commodity thermoplastics through dioxaborolane metathesis
journal, April 2017

Röttger, Max; Domenech, Trystan; van der Weegen, Rob
Science, Vol. 356, Issue 6333
DOI: 10.1126/science.aah5281

Vitrimers: permanent organic networks with glass-like fluidity
journal, January 2016

Denissen, Wim; Winne, Johan M.; Du Prez, Filip E.
Chemical Science, Vol. 7, Issue 1
DOI: 10.1039/C5SC02223A

Catalyst-Free Vitrimers from Vinyl Polymers
journal, February 2019

Lessard, Jacob J.; Garcia, Luis F.; Easterling, Charles P.
Macromolecules, Vol. 52, Issue 5
DOI: 10.1021/acs.macromol.8b02477

Reprocessing and Recycling of Highly Cross-Linked Ion-Conducting Networks through Transalkylation Exchanges of C–N Bonds
journal, April 2015

Obadia, Mona M.; Mudraboyina, Bhanu P.; Serghei, Anatoli
Journal of the American Chemical Society, Vol. 137, Issue 18
DOI: 10.1021/jacs.5b02653

Malleable and Self-Healing Covalent Polymer Networks through Tunable Dynamic Boronic Ester Bonds
journal, May 2015

Cromwell, Olivia R.; Chung, Jaeyoon; Guan, Zhibin
Journal of the American Chemical Society, Vol. 137, Issue 20
DOI: 10.1021/jacs.5b03551

A Surprise from 1954: Siloxane Equilibration Is a Simple, Robust, and Obvious Polymer Self-Healing Mechanism
journal, January 2012

Zheng, Peiwen; McCarthy, Thomas J.
Journal of the American Chemical Society, Vol. 134, Issue 4
DOI: 10.1021/ja2113257

Biobased Amines: From Synthesis to Polymers; Present and Future
journal, October 2016

Froidevaux, Vincent; Negrell, Claire; Caillol, Sylvain
Chemical Reviews, Vol. 116, Issue 22
DOI: 10.1021/acs.chemrev.6b00486

Closed-loop recycling of plastics enabled by dynamic covalent diketoenamine bonds
journal, April 2019

Christensen, Peter R.; Scheuermann, Angelique M.; Loeffler, Kathryn E.
Nature Chemistry, Vol. 11, Issue 5
DOI: 10.1038/s41557-019-0249-2

Mechanically Activated, Catalyst-Free Polyhydroxyurethane Vitrimers
journal, November 2015

Fortman, David J.; Brutman, Jacob P.; Cramer, Christopher J.
Journal of the American Chemical Society, Vol. 137, Issue 44
DOI: 10.1021/jacs.5b08084

Poly(butylene terephthalate)/Glycerol-based Vitrimers via Solid-State Polymerization
journal, August 2017

Zhou, Yanwu; Goossens, Johannes G. P.; Sijbesma, Rint P.
Macromolecules, Vol. 50, Issue 17
DOI: 10.1021/acs.macromol.7b01142

Silyl Ether as a Robust and Thermally Stable Dynamic Covalent Motif for Malleable Polymer Design
journal, October 2017

Nishimura, Yoshio; Chung, Jaeyoon; Muradyan, Hurik
Journal of the American Chemical Society, Vol. 139, Issue 42
DOI: 10.1021/jacs.7b08826

Biobased Thermosetting Epoxy: Present and Future
journal, October 2013

Auvergne, Rémi; Caillol, Sylvain; David, Ghislain
Chemical Reviews, Vol. 114, Issue 2
DOI: 10.1021/cr3001274

Dependence of Effective Molarity on Linker Length for an Intramolecular Protein−Ligand System
journal, February 2007

Krishnamurthy, Vijay M.; Semetey, Vincent; Bracher, Paul J.
Journal of the American Chemical Society, Vol. 129, Issue 5
DOI: 10.1021/ja066780e

Integration of chemical catalysis with extractive fermentation to produce fuels
journal, November 2012

Anbarasan, Pazhamalai; Baer, Zachary C.; Sreekumar, Sanil
Nature, Vol. 491, Issue 7423, p. 235-239
DOI: 10.1038/nature11594

Quantification of the Effect of Conformational Restriction on Supramolecular Effective Molarities
journal, January 2013

Adams, Harry; Chekmeneva, Elena; Hunter, Christopher A.
Journal of the American Chemical Society, Vol. 135, Issue 5
DOI: 10.1021/ja310221t

Heat- or Water-Driven Malleability in a Highly Recyclable Covalent Network Polymer
journal, March 2014

Taynton, Philip; Yu, Kai; Shoemaker, Richard K.
Advanced Materials, Vol. 26, Issue 23
DOI: 10.1002/adma.201400317

Second‐Order Transition Temperatures and Related Properties of Polystyrene. I. Influence of Molecular Weight
journal, June 1950

Fox, Thomas G.; Flory, Paul J.
Journal of Applied Physics, Vol. 21, Issue 6
DOI: 10.1063/1.1699711

Reprocessable polyhydroxyurethane networks exhibiting full property recovery and concurrent associative and dissociative dynamic chemistry via transcarbamoylation and reversible cyclic carbonate aminolysis
journal, January 2017

Chen, Xi; Li, Lingqiao; Jin, Kailong
Polym. Chem., Vol. 8, Issue 41
DOI: 10.1039/C7PY01160A

Polylactide Vitrimers
journal, June 2014

Brutman, Jacob P.; Delgado, Paula A.; Hillmyer, Marc A.
ACS Macro Letters, Vol. 3, Issue 7
DOI: 10.1021/mz500269w

Thermoset Shape-Memory Polyurethane with Intrinsic Plasticity Enabled by Transcarbamoylation
journal, June 2016

Zheng, Ning; Fang, Zizheng; Zou, Weike
Angewandte Chemie International Edition, Vol. 55, Issue 38
DOI: 10.1002/anie.201602847

The Role of Protein Loops and Linkers in Conformational Dynamics and Allostery
journal, February 2016

Papaleo, Elena; Saladino, Giorgio; Lambrughi, Matteo
Chemical Reviews, Vol. 116, Issue 11
DOI: 10.1021/acs.chemrev.5b00623

Vinylogous Urethane Vitrimers
journal, March 2015

Denissen, Wim; Rivero, Guadalupe; Nicolaÿ, Renaud
Advanced Functional Materials, Vol. 25, Issue 16
DOI: 10.1002/adfm.201404553

Similar Records in DOE PAGES and OSTI.GOV collections:

Conformational Entropy as a Means to Control the Behavior of Poly(diketoenamine) Vitrimers In and Out of Equilibrium

Journal Article He, Changfei ; Christensen, Peter R. ; Seguin, Trevor J. ; ... - Angewandte Chemie (International Edition)

Control of equilibrium and non-equilibrium thermomechanical behavior of poly(diketoenamine) vitrimers is shown by incorporating linear polymer segments varying in molecular weight (MW) and conformational degrees of freedom into the dynamic covalent network. While increasing MW of linear segments yields a lower storage modulus at the rubbery plateau after softening above the glass transition (T_g), both T_g and the characteristic time of stress relaxation are independently governed by the conformational entropy of the embodied linear segments. Activation energies for bond exchange in the solid state are lower for networks incorporating flexible chains; the network topology freezing temperature decreases with increasing MWmore »« less
Cited by 2
DOI: 10.1002/anie.201912223

Full Text Available
Poly(oxime–ester) Vitrimers with Catalyst-Free Bond Exchange

Journal Article He, Changfei ; Shi, Shaowei ; Wang, Dong ; ... - Journal of the American Chemical Society

Vitrimers are network polymers that undergo associative bond exchange reactions in the condensed phase above a threshold temperature, dictated by the exchangeable bonds comprising the vitrimer. For vitrimers, chemistries reliant on poorly nucleophilic bond exchange partners (e.g., hydroxy-functionalized alkanes) or poorly electrophilic exchangeable bonds, catalysts are required to lower the threshold temperature, which is undesirable in that catalyst leaching or deactivation diminishes its influence over time and may compromise reuse. Here we show how to access catalyst-free bond exchange reactions in catalyst-dependent polyester vitrimers by obviating conventional ester bonds in favor of oxime-esters. Poly(oxime-ester) (POE) vitrimers are synthesized using thiol-enemore »« less
Cited by 16
DOI: 10.1021/jacs.9b06668

Full Text Available
Unexpected Conformational Behavior of Poly(poly(ethylene glycol) methacrylate)-Poly(propylene carbonate)-Poly(poly(ethylene glycol) methacrylate) (PPEGMA-PPC-PPEGMA) Amphiphilic Block Copolymers in Micellar Solution and at the Air-Water Interface

Journal Article Lee, Jaewon ; Pan, Jingyi ; Chun, Jaehun ; ... - Journal of Colloid and Interface Science

Self-assemblies (bulk micelles and Langmuir monolayers) of a new amphiphilic block copolymer, poly(poly(ethylene glycol) methacrylate)-poly(propylene carbonate)-poly(poly(ethylene glycol) methacrylate) (PPEGMA-PPC-PPEGMA), were investigated in dilute aqueous solution and at the air-water interface. An important feature that distinguishes PPEGMA-PPC-PPEGMA from conventional linear PEG-based polymer surfactants is that in the hydrophilic PPEGMA block the PEG moieties exist as side chains attached to the poly(methacrylate) (PMA) backbone. This study was performed using three PPEGMA-PPC-PPEGMA samples having an identical PPC molecular weight (5.6 kDa) and different PPEGMA molecular weights (7.3, 2.8 and 2.1 kDa on either side) (named as “G7C6G7”, “G3C5G3”, and “G2C6G2”, respectively). Cryo-TEM imagesmore »« less
DOI: 10.1016/j.jcis.2020.01.080
Out of equilibrium: understanding cosmological evolution to lower-entropy states

Journal Article Aguirre, Anthony ; Carroll, Sean M. ; Johnson, Matthew C., E-mail: aguirre@scipp.ucsc.edu, E-mail: seancarroll@gmail.com, E-mail: mjohnson@perimeterinstitute.ca - Journal of Cosmology and Astroparticle Physics

Despite the importance of the Second Law of Thermodynamics, it is not absolute. Statistical mechanics implies that, given sufficient time, systems near equilibrium will spontaneously fluctuate into lower-entropy states, locally reversing the thermodynamic arrow of time. We study the time development of such fluctuations, especially the very large fluctuations relevant to cosmology. Under fairly general assumptions, the most likely history of a fluctuation out of equilibrium is simply the CPT conjugate of the most likely way a system relaxes back to equilibrium. We use this idea to elucidate the spacetime structure of various fluctuations in (stable and metastable) de Sittermore »« less
DOI: 10.1088/1475-7516/2012/02/024
Entanglement entropy and computational complexity of the Anderson impurity model out of equilibrium: Quench dynamics

Journal Article He, Zhuoran ; Millis, Andrew J. - Physical Review B
DOI: 10.1103/PhysRevB.96.085107

Similar Records

Title: Conformational Entropy as a Means to Control the Behavior of Poly(diketoenamine) Vitrimers In and Out of Equilibrium

Citation Formats

Catalyst-Free Thermoset Polyurethane with Permanent Shape Reconfigurability and Highly Tunable Triple-Shape Memory Performance journal, March 2017

A Catalyst-Free Epoxy Vitrimer System Based on Multifunctional Hyperbranched Polymer journal, August 2018

Recyclable, Strong, and Highly Malleable Thermosets Based on Boroxine Networks journal, May 2018

Approaches to Sustainable and Continually Recyclable Cross-Linked Polymers journal, August 2018

Metal-Catalyzed Transesterification for Healing and Assembling of Thermosets journal, April 2012

DNA-Based Nanodevices Controlled by Purely Entropic Linker Domains journal, October 2018

Silica-Like Malleable Materials from Permanent Organic Networks journal, November 2011

Thermoset Shape-Memory Polyurethane with Intrinsic Plasticity Enabled by Transcarbamoylation journal, June 2016

Chemical control of the viscoelastic properties of vinylogous urethane vitrimers journal, March 2017

High-performance vitrimers from commodity thermoplastics through dioxaborolane metathesis journal, April 2017

Vitrimers: permanent organic networks with glass-like fluidity journal, January 2016

Catalyst-Free Vitrimers from Vinyl Polymers journal, February 2019

Reprocessing and Recycling of Highly Cross-Linked Ion-Conducting Networks through Transalkylation Exchanges of C–N Bonds journal, April 2015

Malleable and Self-Healing Covalent Polymer Networks through Tunable Dynamic Boronic Ester Bonds journal, May 2015

A Surprise from 1954: Siloxane Equilibration Is a Simple, Robust, and Obvious Polymer Self-Healing Mechanism journal, January 2012

Biobased Amines: From Synthesis to Polymers; Present and Future journal, October 2016

Closed-loop recycling of plastics enabled by dynamic covalent diketoenamine bonds journal, April 2019

Mechanically Activated, Catalyst-Free Polyhydroxyurethane Vitrimers journal, November 2015

Poly(butylene terephthalate)/Glycerol-based Vitrimers via Solid-State Polymerization journal, August 2017

Silyl Ether as a Robust and Thermally Stable Dynamic Covalent Motif for Malleable Polymer Design journal, October 2017

Biobased Thermosetting Epoxy: Present and Future journal, October 2013

Dependence of Effective Molarity on Linker Length for an Intramolecular Protein−Ligand System journal, February 2007

Integration of chemical catalysis with extractive fermentation to produce fuels journal, November 2012

Quantification of the Effect of Conformational Restriction on Supramolecular Effective Molarities journal, January 2013

Heat- or Water-Driven Malleability in a Highly Recyclable Covalent Network Polymer journal, March 2014

Second‐Order Transition Temperatures and Related Properties of Polystyrene. I. Influence of Molecular Weight journal, June 1950

Reprocessable polyhydroxyurethane networks exhibiting full property recovery and concurrent associative and dissociative dynamic chemistry via transcarbamoylation and reversible cyclic carbonate aminolysis journal, January 2017

Polylactide Vitrimers journal, June 2014

Thermoset Shape-Memory Polyurethane with Intrinsic Plasticity Enabled by Transcarbamoylation journal, June 2016

The Role of Protein Loops and Linkers in Conformational Dynamics and Allostery journal, February 2016

Vinylogous Urethane Vitrimers journal, March 2015

Catalyst-Free Thermoset Polyurethane with Permanent Shape Reconfigurability and Highly Tunable Triple-Shape Memory Performance
journal, March 2017

A Catalyst-Free Epoxy Vitrimer System Based on Multifunctional Hyperbranched Polymer
journal, August 2018

Recyclable, Strong, and Highly Malleable Thermosets Based on Boroxine Networks
journal, May 2018

Approaches to Sustainable and Continually Recyclable Cross-Linked Polymers
journal, August 2018

Metal-Catalyzed Transesterification for Healing and Assembling of Thermosets
journal, April 2012

DNA-Based Nanodevices Controlled by Purely Entropic Linker Domains
journal, October 2018

Silica-Like Malleable Materials from Permanent Organic Networks
journal, November 2011

Thermoset Shape-Memory Polyurethane with Intrinsic Plasticity Enabled by Transcarbamoylation
journal, June 2016

Chemical control of the viscoelastic properties of vinylogous urethane vitrimers
journal, March 2017

High-performance vitrimers from commodity thermoplastics through dioxaborolane metathesis
journal, April 2017

Vitrimers: permanent organic networks with glass-like fluidity
journal, January 2016

Catalyst-Free Vitrimers from Vinyl Polymers
journal, February 2019

Reprocessing and Recycling of Highly Cross-Linked Ion-Conducting Networks through Transalkylation Exchanges of C–N Bonds
journal, April 2015

Malleable and Self-Healing Covalent Polymer Networks through Tunable Dynamic Boronic Ester Bonds
journal, May 2015

A Surprise from 1954: Siloxane Equilibration Is a Simple, Robust, and Obvious Polymer Self-Healing Mechanism
journal, January 2012

Biobased Amines: From Synthesis to Polymers; Present and Future
journal, October 2016

Closed-loop recycling of plastics enabled by dynamic covalent diketoenamine bonds
journal, April 2019

Mechanically Activated, Catalyst-Free Polyhydroxyurethane Vitrimers
journal, November 2015

Poly(butylene terephthalate)/Glycerol-based Vitrimers via Solid-State Polymerization
journal, August 2017

Silyl Ether as a Robust and Thermally Stable Dynamic Covalent Motif for Malleable Polymer Design
journal, October 2017

Biobased Thermosetting Epoxy: Present and Future
journal, October 2013

Dependence of Effective Molarity on Linker Length for an Intramolecular Protein−Ligand System
journal, February 2007

Integration of chemical catalysis with extractive fermentation to produce fuels
journal, November 2012

Quantification of the Effect of Conformational Restriction on Supramolecular Effective Molarities
journal, January 2013

Heat- or Water-Driven Malleability in a Highly Recyclable Covalent Network Polymer
journal, March 2014

Second‐Order Transition Temperatures and Related Properties of Polystyrene. I. Influence of Molecular Weight
journal, June 1950

Reprocessable polyhydroxyurethane networks exhibiting full property recovery and concurrent associative and dissociative dynamic chemistry via transcarbamoylation and reversible cyclic carbonate aminolysis
journal, January 2017

Polylactide Vitrimers
journal, June 2014

Thermoset Shape-Memory Polyurethane with Intrinsic Plasticity Enabled by Transcarbamoylation
journal, June 2016

The Role of Protein Loops and Linkers in Conformational Dynamics and Allostery
journal, February 2016

Vinylogous Urethane Vitrimers
journal, March 2015