Biobased Reprocessable Polyhydroxyurethane Networks

Full Recovery of Crosslink Density with Three Concurrent Dynamic Chemistries

Sumeng Hu, Xi Chen, John M Torkelson*

*Corresponding author for this work

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Despite significant past efforts to exploit green, renewable precursors in polymeric materials and to improve the recyclability and reprocessability of nonisocyanate polyurethane (NIPU) networks, no single study has previously investigated biobased polyhydroxyurethane (PHU) network reprocessability. Renewable, dynamic PHU networks were synthesized by reacting bioderived polyfunctional cyclic carbonates, carbonated soybean oil (CSBO), and sorbitol ether carbonate (SEC), with either a synthetic diamine or a biobased diamine. Network reprocessability was studied by dynamic mechanical analysis. With relatively mild reprocessing conditions, CSBO-based PHU networks exhibit complete recovery of crosslink density and associated properties after multiple melt-state recycling steps. In addition to the presence of reversible cyclic carbonate aminolysis and transcarbamoylation exchange reactions, CSBO-based networks were shown via a model reaction to undergo a third dynamic chemistry based on a transesterification exchange reaction. In contrast to the excellent property recovery achieved by CSBO-based PHU networks, as a result of disadvantageous monomer molecular design, SEC-based networks exhibit poor reprocessability even with increased catalyst load and reprocessing temperature and time. This work reveals the effect of monomer structure on the reprocessability of dynamic polymer networks and highlights the effectiveness of CSBO to serve as a precursor of robust, sustainable NIPU networks with excellent reprocessability.

Original languageEnglish (US)
Pages (from-to)10025-10034
Number of pages10
JournalACS Sustainable Chemistry and Engineering
Volume7
Issue number11
DOIs
StatePublished - Jun 3 2019

Fingerprint

Soybean oil
Soybean Oil
Carbonates
soybean
Recovery
oil
carbonate
Diamines
Polyurethanes
Sorbitol
ether
Ether
Ethers
Monomers
Transesterification
Polymers
Dynamic mechanical analysis
Recycling
recycling
polymer

Keywords

  • Dynamic polymer networks
  • Nonisocyanate polyurethane
  • Renewable materials
  • Reprocessability
  • Sustainability

ASJC Scopus subject areas

  • Chemistry(all)
  • Environmental Chemistry
  • Chemical Engineering(all)
  • Renewable Energy, Sustainability and the Environment

Cite this

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title = "Biobased Reprocessable Polyhydroxyurethane Networks: Full Recovery of Crosslink Density with Three Concurrent Dynamic Chemistries",
abstract = "Despite significant past efforts to exploit green, renewable precursors in polymeric materials and to improve the recyclability and reprocessability of nonisocyanate polyurethane (NIPU) networks, no single study has previously investigated biobased polyhydroxyurethane (PHU) network reprocessability. Renewable, dynamic PHU networks were synthesized by reacting bioderived polyfunctional cyclic carbonates, carbonated soybean oil (CSBO), and sorbitol ether carbonate (SEC), with either a synthetic diamine or a biobased diamine. Network reprocessability was studied by dynamic mechanical analysis. With relatively mild reprocessing conditions, CSBO-based PHU networks exhibit complete recovery of crosslink density and associated properties after multiple melt-state recycling steps. In addition to the presence of reversible cyclic carbonate aminolysis and transcarbamoylation exchange reactions, CSBO-based networks were shown via a model reaction to undergo a third dynamic chemistry based on a transesterification exchange reaction. In contrast to the excellent property recovery achieved by CSBO-based PHU networks, as a result of disadvantageous monomer molecular design, SEC-based networks exhibit poor reprocessability even with increased catalyst load and reprocessing temperature and time. This work reveals the effect of monomer structure on the reprocessability of dynamic polymer networks and highlights the effectiveness of CSBO to serve as a precursor of robust, sustainable NIPU networks with excellent reprocessability.",
keywords = "Dynamic polymer networks, Nonisocyanate polyurethane, Renewable materials, Reprocessability, Sustainability",
author = "Sumeng Hu and Xi Chen and Torkelson, {John M}",
year = "2019",
month = "6",
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doi = "10.1021/acssuschemeng.9b01239",
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TY - JOUR

T1 - Biobased Reprocessable Polyhydroxyurethane Networks

T2 - Full Recovery of Crosslink Density with Three Concurrent Dynamic Chemistries

AU - Hu, Sumeng

AU - Chen, Xi

AU - Torkelson, John M

PY - 2019/6/3

Y1 - 2019/6/3

N2 - Despite significant past efforts to exploit green, renewable precursors in polymeric materials and to improve the recyclability and reprocessability of nonisocyanate polyurethane (NIPU) networks, no single study has previously investigated biobased polyhydroxyurethane (PHU) network reprocessability. Renewable, dynamic PHU networks were synthesized by reacting bioderived polyfunctional cyclic carbonates, carbonated soybean oil (CSBO), and sorbitol ether carbonate (SEC), with either a synthetic diamine or a biobased diamine. Network reprocessability was studied by dynamic mechanical analysis. With relatively mild reprocessing conditions, CSBO-based PHU networks exhibit complete recovery of crosslink density and associated properties after multiple melt-state recycling steps. In addition to the presence of reversible cyclic carbonate aminolysis and transcarbamoylation exchange reactions, CSBO-based networks were shown via a model reaction to undergo a third dynamic chemistry based on a transesterification exchange reaction. In contrast to the excellent property recovery achieved by CSBO-based PHU networks, as a result of disadvantageous monomer molecular design, SEC-based networks exhibit poor reprocessability even with increased catalyst load and reprocessing temperature and time. This work reveals the effect of monomer structure on the reprocessability of dynamic polymer networks and highlights the effectiveness of CSBO to serve as a precursor of robust, sustainable NIPU networks with excellent reprocessability.

AB - Despite significant past efforts to exploit green, renewable precursors in polymeric materials and to improve the recyclability and reprocessability of nonisocyanate polyurethane (NIPU) networks, no single study has previously investigated biobased polyhydroxyurethane (PHU) network reprocessability. Renewable, dynamic PHU networks were synthesized by reacting bioderived polyfunctional cyclic carbonates, carbonated soybean oil (CSBO), and sorbitol ether carbonate (SEC), with either a synthetic diamine or a biobased diamine. Network reprocessability was studied by dynamic mechanical analysis. With relatively mild reprocessing conditions, CSBO-based PHU networks exhibit complete recovery of crosslink density and associated properties after multiple melt-state recycling steps. In addition to the presence of reversible cyclic carbonate aminolysis and transcarbamoylation exchange reactions, CSBO-based networks were shown via a model reaction to undergo a third dynamic chemistry based on a transesterification exchange reaction. In contrast to the excellent property recovery achieved by CSBO-based PHU networks, as a result of disadvantageous monomer molecular design, SEC-based networks exhibit poor reprocessability even with increased catalyst load and reprocessing temperature and time. This work reveals the effect of monomer structure on the reprocessability of dynamic polymer networks and highlights the effectiveness of CSBO to serve as a precursor of robust, sustainable NIPU networks with excellent reprocessability.

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