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Charge-Transfer Complexes as New Inhibitors/Photoinitiators for On-Demand Amine/Peroxide Redox Polymerization

[Image: see text] Redox free-radical polymerizations have widespread applications but still clearly suffer from poor time control of the reaction. Currently, the workability (delay of the gel time) in redox polymerization after mixing is possible thanks to two main types of inhibitors (radical scave...

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Autores principales: Garra, Patxi, Morlet-Savary, Fabrice, Dietlin, Céline, Fouassier, Jean-Pierre, Lalevée, Jacques
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2018
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6644477/
https://www.ncbi.nlm.nih.gov/pubmed/31458852
http://dx.doi.org/10.1021/acsomega.8b00971
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author Garra, Patxi
Morlet-Savary, Fabrice
Dietlin, Céline
Fouassier, Jean-Pierre
Lalevée, Jacques
author_facet Garra, Patxi
Morlet-Savary, Fabrice
Dietlin, Céline
Fouassier, Jean-Pierre
Lalevée, Jacques
author_sort Garra, Patxi
collection PubMed
description [Image: see text] Redox free-radical polymerizations have widespread applications but still clearly suffer from poor time control of the reaction. Currently, the workability (delay of the gel time) in redox polymerization after mixing is possible thanks to two main types of inhibitors (radical scavengers): phenols and nitroxides. Out of this trend, we propose in this work an alternative strategy for time delaying of the redox polymerization, which is based on charge-transfer complexes (CTCs). Thanks to iodonium salt complexation, the amine (here 4-N,N-trimethylaniline) is proposed to be stored in a CTC equilibrium and is slowly released over a period of time (as a result of the consumption of free amines by peroxides). This alternative strategy allowed us to double the gel time (e.g., from 60 to 120 s) while maintaining a high polymerization efficiency (performance comparable to reference nitroxides). More interestingly, the CTCs involved in this retarding strategy are photoresponsive under visible LED@405 nm and can be used on demand as photoinitiators, allowing (i) spectacular increases in polymerization efficiencies (from 50 °C without light to 120 °C under mild irradiation conditions); (ii) drastic reduction of the oxygen-inhibited layer (already 45% C=C conversion at a 2 μm distance from the top surface) compared to the nonirradiated sample (thick inhibited layer of more than 45 μm); and (iii) external control of the redox polymerization gel time due to the possible light activation.
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spelling pubmed-66444772019-08-27 Charge-Transfer Complexes as New Inhibitors/Photoinitiators for On-Demand Amine/Peroxide Redox Polymerization Garra, Patxi Morlet-Savary, Fabrice Dietlin, Céline Fouassier, Jean-Pierre Lalevée, Jacques ACS Omega [Image: see text] Redox free-radical polymerizations have widespread applications but still clearly suffer from poor time control of the reaction. Currently, the workability (delay of the gel time) in redox polymerization after mixing is possible thanks to two main types of inhibitors (radical scavengers): phenols and nitroxides. Out of this trend, we propose in this work an alternative strategy for time delaying of the redox polymerization, which is based on charge-transfer complexes (CTCs). Thanks to iodonium salt complexation, the amine (here 4-N,N-trimethylaniline) is proposed to be stored in a CTC equilibrium and is slowly released over a period of time (as a result of the consumption of free amines by peroxides). This alternative strategy allowed us to double the gel time (e.g., from 60 to 120 s) while maintaining a high polymerization efficiency (performance comparable to reference nitroxides). More interestingly, the CTCs involved in this retarding strategy are photoresponsive under visible LED@405 nm and can be used on demand as photoinitiators, allowing (i) spectacular increases in polymerization efficiencies (from 50 °C without light to 120 °C under mild irradiation conditions); (ii) drastic reduction of the oxygen-inhibited layer (already 45% C=C conversion at a 2 μm distance from the top surface) compared to the nonirradiated sample (thick inhibited layer of more than 45 μm); and (iii) external control of the redox polymerization gel time due to the possible light activation. American Chemical Society 2018-06-25 /pmc/articles/PMC6644477/ /pubmed/31458852 http://dx.doi.org/10.1021/acsomega.8b00971 Text en Copyright © 2018 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
spellingShingle Garra, Patxi
Morlet-Savary, Fabrice
Dietlin, Céline
Fouassier, Jean-Pierre
Lalevée, Jacques
Charge-Transfer Complexes as New Inhibitors/Photoinitiators for On-Demand Amine/Peroxide Redox Polymerization
title Charge-Transfer Complexes as New Inhibitors/Photoinitiators for On-Demand Amine/Peroxide Redox Polymerization
title_full Charge-Transfer Complexes as New Inhibitors/Photoinitiators for On-Demand Amine/Peroxide Redox Polymerization
title_fullStr Charge-Transfer Complexes as New Inhibitors/Photoinitiators for On-Demand Amine/Peroxide Redox Polymerization
title_full_unstemmed Charge-Transfer Complexes as New Inhibitors/Photoinitiators for On-Demand Amine/Peroxide Redox Polymerization
title_short Charge-Transfer Complexes as New Inhibitors/Photoinitiators for On-Demand Amine/Peroxide Redox Polymerization
title_sort charge-transfer complexes as new inhibitors/photoinitiators for on-demand amine/peroxide redox polymerization
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6644477/
https://www.ncbi.nlm.nih.gov/pubmed/31458852
http://dx.doi.org/10.1021/acsomega.8b00971
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