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RAFT Polymerisation and Hypercrosslinking Improve Crosslink Homogeneity and Surface Area of Styrene Based PolyHIPEs

The influence of a polymerisation mechanism (reversible addition–fragmentation chain transfer; RAFT vs. free radical polymerisation; FRP) on the porous structure of highly porous poly(styrene-co-divinylbenzene) polymers was investigated. The highly porous polymers were synthesised via high internal...

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Autores principales: Koler, Amadeja, Brus, Jiři, Krajnc, Peter
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10222607/
https://www.ncbi.nlm.nih.gov/pubmed/37242829
http://dx.doi.org/10.3390/polym15102255
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author Koler, Amadeja
Brus, Jiři
Krajnc, Peter
author_facet Koler, Amadeja
Brus, Jiři
Krajnc, Peter
author_sort Koler, Amadeja
collection PubMed
description The influence of a polymerisation mechanism (reversible addition–fragmentation chain transfer; RAFT vs. free radical polymerisation; FRP) on the porous structure of highly porous poly(styrene-co-divinylbenzene) polymers was investigated. The highly porous polymers were synthesised via high internal phase emulsion templating (polymerizing the continuous phase of a high internal phase emulsion), utilising either FRP or RAFT processes. Furthermore, residual vinyl groups in the polymer chains were used for the subsequent crosslinking (hypercrosslinking) applying di-tert-butyl peroxide as the source of radicals. A significant difference in the specific surface area of polymers prepared by FRP (between 20 and 35 m(2)/g) and samples prepared by RAFT polymerisation (between 60 and 150 m(2)/g) was found. Based on the results from gas adsorption and solid state NMR, it could be concluded that the RAFT polymerisation affects the homogeneous distribution of the crosslinks in the highly crosslinked styrene-co-divinylbenzene polymer network. During the initial crosslinking, RAFT polymerisation leads to the increase in mesopores with diameters between 2 and 20 nm, resulting in good accessibility of polymer chains during the hypercrosslinking reaction, which is reflected in increased microporosity. The fraction of micropores created during the hypercrosslinking of polymers prepared via RAFT is around 10% of the total pore volume, which is up to 10 times more than for polymers prepared by FRP. Specific surface area, mesopore surface area, and total pore volume after hypercrosslinking reach almost the same values, regardless of the initial crosslinking. The degree of hypercrosslinking was confirmed by determination of the remaining double bonds by solid-state NMR analysis.
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spelling pubmed-102226072023-05-28 RAFT Polymerisation and Hypercrosslinking Improve Crosslink Homogeneity and Surface Area of Styrene Based PolyHIPEs Koler, Amadeja Brus, Jiři Krajnc, Peter Polymers (Basel) Article The influence of a polymerisation mechanism (reversible addition–fragmentation chain transfer; RAFT vs. free radical polymerisation; FRP) on the porous structure of highly porous poly(styrene-co-divinylbenzene) polymers was investigated. The highly porous polymers were synthesised via high internal phase emulsion templating (polymerizing the continuous phase of a high internal phase emulsion), utilising either FRP or RAFT processes. Furthermore, residual vinyl groups in the polymer chains were used for the subsequent crosslinking (hypercrosslinking) applying di-tert-butyl peroxide as the source of radicals. A significant difference in the specific surface area of polymers prepared by FRP (between 20 and 35 m(2)/g) and samples prepared by RAFT polymerisation (between 60 and 150 m(2)/g) was found. Based on the results from gas adsorption and solid state NMR, it could be concluded that the RAFT polymerisation affects the homogeneous distribution of the crosslinks in the highly crosslinked styrene-co-divinylbenzene polymer network. During the initial crosslinking, RAFT polymerisation leads to the increase in mesopores with diameters between 2 and 20 nm, resulting in good accessibility of polymer chains during the hypercrosslinking reaction, which is reflected in increased microporosity. The fraction of micropores created during the hypercrosslinking of polymers prepared via RAFT is around 10% of the total pore volume, which is up to 10 times more than for polymers prepared by FRP. Specific surface area, mesopore surface area, and total pore volume after hypercrosslinking reach almost the same values, regardless of the initial crosslinking. The degree of hypercrosslinking was confirmed by determination of the remaining double bonds by solid-state NMR analysis. MDPI 2023-05-10 /pmc/articles/PMC10222607/ /pubmed/37242829 http://dx.doi.org/10.3390/polym15102255 Text en © 2023 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Koler, Amadeja
Brus, Jiři
Krajnc, Peter
RAFT Polymerisation and Hypercrosslinking Improve Crosslink Homogeneity and Surface Area of Styrene Based PolyHIPEs
title RAFT Polymerisation and Hypercrosslinking Improve Crosslink Homogeneity and Surface Area of Styrene Based PolyHIPEs
title_full RAFT Polymerisation and Hypercrosslinking Improve Crosslink Homogeneity and Surface Area of Styrene Based PolyHIPEs
title_fullStr RAFT Polymerisation and Hypercrosslinking Improve Crosslink Homogeneity and Surface Area of Styrene Based PolyHIPEs
title_full_unstemmed RAFT Polymerisation and Hypercrosslinking Improve Crosslink Homogeneity and Surface Area of Styrene Based PolyHIPEs
title_short RAFT Polymerisation and Hypercrosslinking Improve Crosslink Homogeneity and Surface Area of Styrene Based PolyHIPEs
title_sort raft polymerisation and hypercrosslinking improve crosslink homogeneity and surface area of styrene based polyhipes
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10222607/
https://www.ncbi.nlm.nih.gov/pubmed/37242829
http://dx.doi.org/10.3390/polym15102255
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