Recyclable dual-curing thiol-isocyanate-epoxy vitrimers with sequential relaxation profiles
Two series of poly(thiourethane)s-poly(thiol-epoxy) hybrids were prepared from dual-curing, stoichiometric thiol:isocyanate:epoxy mixtures. 1-methylimidazole (MI) was used as initiator for the thiol-isocyanate and thiol-epoxy curing reactions. A salt of tetraphenylborate derived from highly basic am...
| Autores: | , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2023 |
| País: | España |
| Institución: | Universitat Politècnica de Catalunya (UPC) |
| Repositorio: | UPCommons. Portal del coneixement obert de la UPC |
| Idioma: | inglés |
| OAI Identifier: | oai:upcommons.upc.edu:2117/392464 |
| Acceso en línea: | https://hdl.handle.net/2117/392464 https://dx.doi.org/10.1016/j.eurpolymj.2023.112290 |
| Access Level: | acceso abierto |
| Palabra clave: | Polymers -- Thermal properties Epoxy compounds Thermoplastics Thermosetting plastics Vitrimers Poly(thiourethane) Isocyanate Dual-curing Thermosets Recycling Epoxy Thiol Polímers -- Propietats tèrmiques Epòxids Termoplàstics Plàstics termoenduribles Àrees temàtiques de la UPC::Enginyeria dels materials::Materials plàstics i polímers Àrees temàtiques de la UPC::Física::Termodinàmica |
| Sumario: | Two series of poly(thiourethane)s-poly(thiol-epoxy) hybrids were prepared from dual-curing, stoichiometric thiol:isocyanate:epoxy mixtures. 1-methylimidazole (MI) was used as initiator for the thiol-isocyanate and thiol-epoxy curing reactions. A salt of tetraphenylborate derived from highly basic amine 1,5,7 triazabicyclo [4,4,0]dec-5-ene (TBD) was used as catalyst for the activation of bond exchange reactions. The curing kinetics and the glass transition temperature (Tg) of the samples were studied by differential scanning calorimetry (DSC). Thermal stability was characterized by thermogravimetric analysis (TGA). Stress relaxation dynamics related to the bond exchange reactions were studied by dynamic mechanical analysis (DMA). Recyclability of the fully cured samples according to the DMA results was carried out by hot-pressing at elevated temperatures. The results show that the curing process takes place in a controlled and sequential way: the thiol-isocyanate reaction takes place first, at moderate temperatures, followed by the thiol-epoxy reaction, which is completed at higher temperatures. The analysis of stress relaxation evidences a complex two-step relaxation behavior depending on the contribution of isocyanate and epoxy groups to the mixture. Isocyanate-rich materials show a simple relaxation process corresponding to the trans-thiocarbamoylation exchange reactions. Epoxy-rich materials show, in contrast, a two-step relaxation processes evidencing that trans-thiocarbamoylation alone may not be sufficient to relax the stress completely, due to an apparently permanent network structure. However, complete stress relaxation is possible for epoxy-rich materials through additional bond exchange reactions such as transesterification or dynamic thiol-Michael, but at a slower rate. Depending on the composition and the temperature, full recycling of the material can be achieved at moderate temperatures in a timescale of minutes to hours. |
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