Architecture-Controlled Ring-Opening Polymerization for Dynamic Covalent Poly(disulfide)s

Liu, Yun; Jia, Yuan; Wu, Qiong; Moore, Jeffrey S.

doi:10.1021/jacs.9b08957

Title: Architecture-Controlled Ring-Opening Polymerization for Dynamic Covalent Poly(disulfide)s

Abstract

A strategy is discussed for controlling the architecture of poly(disulfide)s by ring-opening polymerization. Aryl thiol initiators shift the ring-chain equilibrium to yield cyclic pol-ymers while alkyl thiols favor linear ones. Control over polymerization enables synthesis of high polymers (630 kDa) and catalytic depolymerization to recycle monomers. Our research offers a new avenue to create dynamic covalent poly-mers with controlled geometry and length, allowing better characterization of structure-property relationships to expand their materials potentials.

Authors:

^[1]; Jia, Yuan ^[1];

^[1];

^[1]

Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Illinois at Urbana-Champaign, IL (United States)

Publication Date:: Fri Oct 11 00:00:00 EDT 2019

Research Org.:: Univ. of Illinois at Urbana-Champaign, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Contributing Org.:: Joint Center for Energy Storage Research (JCESR)

OSTI Identifier:: 1600687

Grant/Contract Number:: AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Volume: 141; Journal Issue: 43; Journal ID: ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Liu, Yun, Jia, Yuan, Wu, Qiong, and Moore, Jeffrey S. Architecture-Controlled Ring-Opening Polymerization for Dynamic Covalent Poly(disulfide)s.  United States: N. p., 2019. 
Web.  doi:10.1021/jacs.9b08957.

Copy to clipboard


                    Liu, Yun, Jia, Yuan, Wu, Qiong, & Moore, Jeffrey S. Architecture-Controlled Ring-Opening Polymerization for Dynamic Covalent Poly(disulfide)s.  United States.  https://doi.org/10.1021/jacs.9b08957

Copy to clipboard


                    Liu, Yun, Jia, Yuan, Wu, Qiong, and Moore, Jeffrey S. Fri .  
"Architecture-Controlled Ring-Opening Polymerization for Dynamic Covalent Poly(disulfide)s".  United States.  https://doi.org/10.1021/jacs.9b08957.  https://www.osti.gov/servlets/purl/1600687.

Copy to clipboard


                    
@article{osti_1600687,

  title        = {Architecture-Controlled Ring-Opening Polymerization for Dynamic Covalent Poly(disulfide)s},

  author       = {Liu, Yun and Jia, Yuan and Wu, Qiong and Moore, Jeffrey S.},

  abstractNote = {A strategy is discussed for controlling the architecture of poly(disulfide)s by ring-opening polymerization. Aryl thiol initiators shift the ring-chain equilibrium to yield cyclic pol-ymers while alkyl thiols favor linear ones. Control over polymerization enables synthesis of high polymers (630 kDa) and catalytic depolymerization to recycle monomers. Our research offers a new avenue to create dynamic covalent poly-mers with controlled geometry and length, allowing better characterization of structure-property relationships to expand their materials potentials.},

  doi          = {10.1021/jacs.9b08957},

  journal      = {Journal of the American Chemical Society},

  number       = 43,

  volume       = 141,

  place        = {United States},

  year         = {Fri Oct 11 00:00:00 EDT 2019},

  month        = {Fri Oct 11 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/jacs.9b08957

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 80 works

Citation information provided by
Web of Science

Figures / Tables:

Scheme 1: Methods for the Synthesis of Poly(Disulfide)s

All figures and tables (6 total)

Save / Share:

Export Metadata

Save to My Library

Figures / Tables found in this record:

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

Similar Records in DOE PAGES and OSTI.GOV collections:

Amidine-Mediated Zwitterionic Ring-Opening Polymerization of N -Alkyl N -Carboxyanhydride: Mechanism, Kinetics, and Architecture Elucidation

Journal Article Li, Ang ; Lu, Lu ; Li, Xin ; ... - Macromolecules

Zwitterionic ring-opening polymerization (ZROP) of N-butyl N-carboxyanhydrides (Bu-NCAs) has been investigated using 1,8-diazabicycloundec-7-ene (DBU), a bicyclic amidine initiator. It was found that poly(N-butylglycine)s (PNBGs) with molecular weight (M_n) in the 3.5–32.4 kg mol–1 range and polydispersity index (PDI) in the 1.02–1.12 range can be readily obtained by systematically varying the initial monomer to initiator feed ratio. The polymerization exhibits characteristics of a controlled polymerization, as evidenced by the linear increase of polymer molecular weight with conversion and the successful enchainment experiments. Kinetic studies have shown that the reaction is first-order dependent on the monomer and the DBU concentration. The ratemore »« less
https://doi.org/10.1021/acs.macromol.5b02611
Amidine-Mediated Zwitterionic Ring-Opening Polymerization of N-Alkyl N-Carboxyanhydride: Mechanism, Kinetics, and Architecture Elucidation

Journal Article Li, Ang ; Lu, Lu ; Li, Xin ; ... - Macromolecules

Zwitterionic ring-opening polymerization (ZROP) of N-butyl N-carboxyanhydrides (Bu-NCAs) has been investigated using 1,8-diazabicycloundec-7-ene (DBU), a bicyclic amidine initiator. It was found that poly(N-butylglycine)s (PNBGs) with molecular weight (M_n) in the 3.5–32.4 kg mol^–1 range and polydispersity index (PDI) in the 1.02–1.12 range can be readily obtained by systematically varying the initial monomer to initiator feed ratio. The polymerization exhibits characteristics of a controlled polymerization, as evidenced by the linear increase of polymer molecular weight with conversion and the successful enchainment experiments. Kinetic studies revealed that the reaction is first-order dependent on the monomer and the DBU concentration. The rate ofmore »« less
Cited by 46
https://doi.org/10.1021/acs.macromol.5b02611

Full Text Available
Poly(3-hexylthiophene) Molecular Bottlebrushes via Ring-Opening Metathesis Polymerization: Macromolecular Architecture Enhanced Aggregation

Journal Article Ahn, Suk-kyun ; Pickel, Deanna L. ; Kochemba, W. Michael ; ... - ACS Macro Letters

We report a facile synthetic strategy based on a grafting through approach to prepare well-defined molecular bottlebrushes composed of regioregular poly(3-hexylthiophene) (rr-P3HT) as the conjugated polymeric side chain. To this end, the exo-norbornenyl-functionalized P3HT macromonomer was synthesized by Kumada catalyst transfer polycondensation (KCTP) followed by postpolymerization modifications, and the resulting conjugated macromonomer was successfully polymerized by ring-opening metathesis polymerization (ROMP) in a controlled manner. The P3HT molecular bottlebrushes display an unprecedented strong physical aggregation upon drying during recovery, as verified by several analyses of the solution and solid states. This remarkably strong aggregation behavior is attributed to a significant enhancementmore »« less
https://doi.org/10.1021/mz4003563
ipso ‐Arylative Ring‐Opening Polymerization as a Route to Electron‐Deficient Conjugated Polymers

Journal Article Shih, Feng‐Yang ; Choi, Deokkyu ; Wu, Qin ; ... - Angewandte Chemie

Abstract ipso ‐Arylative ring‐opening polymerization of 2‐bromo‐8‐aryl‐8 H ‐indeno[2,1‐b]thiophen‐8‐ol monomers proceeds to M _n up to 9 kg mol ⁻¹ with conversion of the monomer diarylcarbinol groups to pendent conjugated aroylphenyl side chains (2‐benzoylphenyl or 2‐(4‐hexylbenzoyl)phenyl), which influence the optical and electronic properties of the resulting polythiophenes. Poly(3‐(2‐(4‐hexylbenzoyl)phenyl)thiophene) was found to have lower frontier orbital energy levels (HOMO/LUMO=−5.9/−4.0 eV) than poly(3‐hexylthiophene) owing to the electron‐withdrawing ability of the aryl ketone side chains. The electron mobility (ca. 2×10 ⁻³ cm ² V ⁻¹ s ⁻¹ ) for poly(3‐(2‐(4‐hexylbenzoyl)phenyl)thiophene) was found to be significantly higher than the hole mobility (ca. 8×10 ⁻⁶ cm ² Vmore »« less
https://doi.org/10.1002/ange.201809610
ipso-Arylative Ring-Opening Polymerization as a Route to Electron-Deficient Conjugated Polymers

Journal Article Shih, Feng -Yang ; Choi, Deokkyu ; Wu, Qin ; ... - Angewandte Chemie (International Edition)

Abstract ipso ‐Arylative ring‐opening polymerization of 2‐bromo‐8‐aryl‐8 H ‐indeno[2,1‐b]thiophen‐8‐ol monomers proceeds to M _n up to 9 kg mol ⁻¹ with conversion of the monomer diarylcarbinol groups to pendent conjugated aroylphenyl side chains (2‐benzoylphenyl or 2‐(4‐hexylbenzoyl)phenyl), which influence the optical and electronic properties of the resulting polythiophenes. Poly(3‐(2‐(4‐hexylbenzoyl)phenyl)thiophene) was found to have lower frontier orbital energy levels (HOMO/LUMO=−5.9/−4.0 eV) than poly(3‐hexylthiophene) owing to the electron‐withdrawing ability of the aryl ketone side chains. The electron mobility (ca. 2×10 ⁻³ cm ² V ⁻¹ s ⁻¹ ) for poly(3‐(2‐(4‐hexylbenzoyl)phenyl)thiophene) was found to be significantly higher than the hole mobility (ca. 8×10 ⁻⁶ cm ² Vmore »« less
Cited by 3
https://doi.org/10.1002/anie.201809610

Full Text Available

Similar Records