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Conformational variations for surface-initiated reversible deactivation radical polymerization : from flat to curved nanoparticle surfaces

(2021) MACROMOLECULES. 54(18). p.8270-8288
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Abstract
Although progress in surface-initiated reversible deactivation radical polymerization (SI-RDRP) has already enabled the production of increasingly novel and advanced polymer structures on solid surfaces, fundamental kinetic questions remain regarding the impact of reaction conditions on the molecular properties of synthesized tethered chains. In the current work, we put forward a matrix-based kinetic Monte Carlo (kMC) model, which is based on an implicit SI-RDRP reaction scheme and continuous three-dimensional (3D) representations, capable of following the temporal evolution of the molecular properties of individual free and surface-tethered polymer chains. This is uniquely possible for variable surface curvature (nanoparticle radii from 4.5 to 32 nm; 353 K; monomer: methyl methacrylate), also including the comparison with the limiting case of a flat surface and addressing various (average) RDRP initiator surface coverages. For the tethered chains, we emphasize the prediction of the variation of the molecular height, monomer occupancy, and radius of gyration and also focus on the simulation of the chain length distribution (CLD) to enable a comparison with solution RDRP results. It is shown that confinement effects on the surface lead to the formation of heterogeneous polymer layers with a marked bimodality in the number CLD. This bimodality is, however, wiped out in experimental analysis based on log-molar mass distributions. It is also shown that an increase in the size of the spherical particles and, hence, a decrease in their curvature results in a deterioration of the control over molecular properties, leading to behavior more similar to that of flat surfaces. Average molecular heights and monomer occupancies can vary with a factor of 2. The impact of the targeted chain length is shown to be of lower importance.
Keywords
Materials Chemistry, Inorganic Chemistry, Polymers and Plastics, Organic Chemistry

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MLA
Arraez Hernandez, Francisco Jose, et al. “Conformational Variations for Surface-Initiated Reversible Deactivation Radical Polymerization : From Flat to Curved Nanoparticle Surfaces.” MACROMOLECULES, vol. 54, no. 18, 2021, pp. 8270–88, doi:10.1021/acs.macromol.1c00855.
APA
Arraez Hernandez, F. J., Van Steenberge, P., Sobieski, J., Matyjaszewski, K., & D’hooge, D. (2021). Conformational variations for surface-initiated reversible deactivation radical polymerization : from flat to curved nanoparticle surfaces. MACROMOLECULES, 54(18), 8270–8288. https://doi.org/10.1021/acs.macromol.1c00855
Chicago author-date
Arraez Hernandez, Francisco Jose, Paul Van Steenberge, Julian Sobieski, Krzysztof Matyjaszewski, and Dagmar D’hooge. 2021. “Conformational Variations for Surface-Initiated Reversible Deactivation Radical Polymerization : From Flat to Curved Nanoparticle Surfaces.” MACROMOLECULES 54 (18): 8270–88. https://doi.org/10.1021/acs.macromol.1c00855.
Chicago author-date (all authors)
Arraez Hernandez, Francisco Jose, Paul Van Steenberge, Julian Sobieski, Krzysztof Matyjaszewski, and Dagmar D’hooge. 2021. “Conformational Variations for Surface-Initiated Reversible Deactivation Radical Polymerization : From Flat to Curved Nanoparticle Surfaces.” MACROMOLECULES 54 (18): 8270–8288. doi:10.1021/acs.macromol.1c00855.
Vancouver
1.
Arraez Hernandez FJ, Van Steenberge P, Sobieski J, Matyjaszewski K, D’hooge D. Conformational variations for surface-initiated reversible deactivation radical polymerization : from flat to curved nanoparticle surfaces. MACROMOLECULES. 2021;54(18):8270–88.
IEEE
[1]
F. J. Arraez Hernandez, P. Van Steenberge, J. Sobieski, K. Matyjaszewski, and D. D’hooge, “Conformational variations for surface-initiated reversible deactivation radical polymerization : from flat to curved nanoparticle surfaces,” MACROMOLECULES, vol. 54, no. 18, pp. 8270–8288, 2021.
@article{8723756,
  abstract     = {{Although progress in surface-initiated reversible deactivation radical polymerization (SI-RDRP) has already enabled the production of increasingly novel and advanced polymer structures on solid surfaces, fundamental kinetic questions remain regarding the impact of reaction conditions on the molecular properties of synthesized tethered chains. In the current work, we put forward a matrix-based kinetic Monte Carlo (kMC) model, which is based on an implicit SI-RDRP reaction scheme and continuous three-dimensional (3D) representations, capable of following the temporal evolution of the molecular properties of individual free and surface-tethered polymer chains. This is uniquely possible for variable surface curvature (nanoparticle radii from 4.5 to 32 nm; 353 K; monomer: methyl methacrylate), also including the comparison with the limiting case of a flat surface and addressing various (average) RDRP initiator surface coverages. For the tethered chains, we emphasize the prediction of the variation of the molecular height, monomer occupancy, and radius of gyration and also focus on the simulation of the chain length distribution (CLD) to enable a comparison with solution RDRP results. It is shown that confinement effects on the surface lead to the formation of heterogeneous polymer layers with a marked bimodality in the number CLD. This bimodality is, however, wiped out in experimental analysis based on log-molar mass distributions. It is also shown that an increase in the size of the spherical particles and, hence, a decrease in their curvature results in a deterioration of the control over molecular properties, leading to behavior more similar to that of flat surfaces. Average molecular heights and monomer occupancies can vary with a factor of 2. The impact of the targeted chain length is shown to be of lower importance.}},
  author       = {{Arraez Hernandez, Francisco Jose and Van Steenberge, Paul and Sobieski, Julian and Matyjaszewski, Krzysztof and D'hooge, Dagmar}},
  issn         = {{0024-9297}},
  journal      = {{MACROMOLECULES}},
  keywords     = {{Materials Chemistry,Inorganic Chemistry,Polymers and Plastics,Organic Chemistry}},
  language     = {{eng}},
  number       = {{18}},
  pages        = {{8270--8288}},
  title        = {{Conformational variations for surface-initiated reversible deactivation radical polymerization : from flat to curved nanoparticle surfaces}},
  url          = {{http://doi.org/10.1021/acs.macromol.1c00855}},
  volume       = {{54}},
  year         = {{2021}},
}

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