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Connecting polymer synthesis and chemical recycling on a chain-by-chain basis : a unified matrix-based kinetic Monte Carlo strategy

Kyann De Smit (UGent) , Yoshi Marien (UGent) , Kevin Van Geem (UGent) , Paul Van Steenberge (UGent) and Dagmar D'hooge (UGent)
(2020) REACTION CHEMISTRY & ENGINEERING. 5(10). p.1909-1928
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Abstract
One of the challenges faced by modern society is the realization of a circular economy for polymer products. A bottleneck is the understanding of (co)polymer synthesis and degradation routes on a chain-by-chain basis, as the location of specific functional groups or structural defects determines the distributed chemical nature of the macrospecies involved and thus the reaction possibilities and macroscopic properties. Here, we present a unified matrix-based elementary step driven kinetic Monte Carlo (kMC) strategy to fully connect polymer synthesis and subsequent degradation at the molecular level, aiming at the recovery of the original monomer or a product spectrum of oligomers either degradable or upcyclable into high value-added products. This kMC strategy is illustrated for radical polymerization with methyl methacrylate (MMA) as the main monomer, selecting two case studies: (i) radical polymerization of MMA and the subsequent thermal degradation back to this monomer; and (ii) radical copolymerization of MMA with 2-methylene-1,3-dioxepane (MDO) and the subsequent hydrolysis of the resulting poly(MMA–MDO) toward biodegradable oligomers. For the first case study, it is shown that the shape and location of the log-molar mass distribution strongly affects the degradation efficiency. For the second case study, it is highlighted that the inherent molecular heterogeneity of copolymers strongly defines the framework in which degradation synthesis routes can be exploited.
Keywords
FREE-RADICAL POLYMERIZATION, EVALUATED RATE COEFFICIENTS, PROPAGATION RATE COEFFICIENTS, TERMINATION RATE COEFFICIENTS, METHYL-METHACRYLATE MMA, POLY(METHYL METHACRYLATE), THERMAL-DEGRADATION, PULSED-LASER, OXIDATIVE-DEGRADATION, RAFT POLYMERIZATION

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MLA
De Smit, Kyann, et al. “Connecting Polymer Synthesis and Chemical Recycling on a Chain-by-Chain Basis : A Unified Matrix-Based Kinetic Monte Carlo Strategy.” REACTION CHEMISTRY & ENGINEERING, vol. 5, no. 10, 2020, pp. 1909–28, doi:10.1039/d0re00266f.
APA
De Smit, K., Marien, Y., Van Geem, K., Van Steenberge, P., & D’hooge, D. (2020). Connecting polymer synthesis and chemical recycling on a chain-by-chain basis : a unified matrix-based kinetic Monte Carlo strategy. REACTION CHEMISTRY & ENGINEERING, 5(10), 1909–1928. https://doi.org/10.1039/d0re00266f
Chicago author-date
De Smit, Kyann, Yoshi Marien, Kevin Van Geem, Paul Van Steenberge, and Dagmar D’hooge. 2020. “Connecting Polymer Synthesis and Chemical Recycling on a Chain-by-Chain Basis : A Unified Matrix-Based Kinetic Monte Carlo Strategy.” REACTION CHEMISTRY & ENGINEERING 5 (10): 1909–28. https://doi.org/10.1039/d0re00266f.
Chicago author-date (all authors)
De Smit, Kyann, Yoshi Marien, Kevin Van Geem, Paul Van Steenberge, and Dagmar D’hooge. 2020. “Connecting Polymer Synthesis and Chemical Recycling on a Chain-by-Chain Basis : A Unified Matrix-Based Kinetic Monte Carlo Strategy.” REACTION CHEMISTRY & ENGINEERING 5 (10): 1909–1928. doi:10.1039/d0re00266f.
Vancouver
1.
De Smit K, Marien Y, Van Geem K, Van Steenberge P, D’hooge D. Connecting polymer synthesis and chemical recycling on a chain-by-chain basis : a unified matrix-based kinetic Monte Carlo strategy. REACTION CHEMISTRY & ENGINEERING. 2020;5(10):1909–28.
IEEE
[1]
K. De Smit, Y. Marien, K. Van Geem, P. Van Steenberge, and D. D’hooge, “Connecting polymer synthesis and chemical recycling on a chain-by-chain basis : a unified matrix-based kinetic Monte Carlo strategy,” REACTION CHEMISTRY & ENGINEERING, vol. 5, no. 10, pp. 1909–1928, 2020.
@article{8675918,
  abstract     = {One of the challenges faced by modern society is the realization of a circular economy for polymer products. A bottleneck is the understanding of (co)polymer synthesis and degradation routes on a chain-by-chain basis, as the location of specific functional groups or structural defects determines the distributed chemical nature of the macrospecies involved and thus the reaction possibilities and macroscopic properties. Here, we present a unified matrix-based elementary step driven kinetic Monte Carlo (kMC) strategy to fully connect polymer synthesis and subsequent degradation at the molecular level, aiming at the recovery of the original monomer or a product spectrum of oligomers either degradable or upcyclable into high value-added products. This kMC strategy is illustrated for radical polymerization with methyl methacrylate (MMA) as the main monomer, selecting two case studies: (i) radical polymerization of MMA and the subsequent thermal degradation back to this monomer; and (ii) radical copolymerization of MMA with 2-methylene-1,3-dioxepane (MDO) and the subsequent hydrolysis of the resulting poly(MMA–MDO) toward biodegradable oligomers. For the first case study, it is shown that the shape and location of the log-molar mass distribution strongly affects the degradation efficiency. For the second case study, it is highlighted that the inherent molecular heterogeneity of copolymers strongly defines the framework in which degradation synthesis routes can be exploited.},
  author       = {De Smit, Kyann and Marien, Yoshi and Van Geem, Kevin and Van Steenberge, Paul and D'hooge, Dagmar},
  issn         = {2058-9883},
  journal      = {REACTION CHEMISTRY & ENGINEERING},
  keywords     = {FREE-RADICAL POLYMERIZATION,EVALUATED RATE COEFFICIENTS,PROPAGATION RATE COEFFICIENTS,TERMINATION RATE COEFFICIENTS,METHYL-METHACRYLATE MMA,POLY(METHYL METHACRYLATE),THERMAL-DEGRADATION,PULSED-LASER,OXIDATIVE-DEGRADATION,RAFT POLYMERIZATION},
  language     = {eng},
  number       = {10},
  pages        = {1909--1928},
  title        = {Connecting polymer synthesis and chemical recycling on a chain-by-chain basis : a unified matrix-based kinetic Monte Carlo strategy},
  url          = {http://dx.doi.org/10.1039/d0re00266f},
  volume       = {5},
  year         = {2020},
}

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