Cargando…

Recyclable Organocatalyzed Poly(Thiourethane) Covalent Adaptable Networks

A new type of tetraphenylborate salts derived from highly basic and nucleophilic amines, namely 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU) and triazabicyclodecene (TBD), was applied to the preparation of networked poly(thiourethane)s (PTUs), which showed a vitri...

Descripción completa

Detalles Bibliográficos
Autores principales: Gamardella, Francesco, Muñoz, Sara, De la Flor, Silvia, Ramis, Xavier, Serra, Angels
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7761908/
https://www.ncbi.nlm.nih.gov/pubmed/33291704
http://dx.doi.org/10.3390/polym12122913
_version_ 1783627679042371584
author Gamardella, Francesco
Muñoz, Sara
De la Flor, Silvia
Ramis, Xavier
Serra, Angels
author_facet Gamardella, Francesco
Muñoz, Sara
De la Flor, Silvia
Ramis, Xavier
Serra, Angels
author_sort Gamardella, Francesco
collection PubMed
description A new type of tetraphenylborate salts derived from highly basic and nucleophilic amines, namely 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU) and triazabicyclodecene (TBD), was applied to the preparation of networked poly(thiourethane)s (PTUs), which showed a vitrimer-like behavior, with higher stress-relaxation rates than PTUs prepared by using dibutyl thin dilaurate (DBTDL) as the catalyst. The use of these salts, which release the amines when heated, instead of the pure amines, allows the formulation to be easily manipulated to prepare any type of samples. The materials prepared from stoichiometric mixtures of hexamethylene diisocyanate (HDI), trithiol (S3) and with a 10% of molar excess of isocyanate or thiol were characterized by FTIR, thermomechanical analysis, thermogravimetry, stress-relaxation tests and tensile tests, thus obtaining a complete thermal and mechanical characterization of the materials. The recycled materials obtained by grinding the original PTUs and hot-pressing the small pieces in the optimized time and temperature conditions were fully characterized by mechanical, thermomechanical and FTIR studies. This allowed us to confirm their recyclability, without appreciable changes in the network structure and performance. From several observations, the dissociative interchange trans-thiocarbamoylation mechanism was evidenced as the main responsible of the topological rearrangements at high temperature, resulting in a vitrimeric-like behavior.
format Online
Article
Text
id pubmed-7761908
institution National Center for Biotechnology Information
language English
publishDate 2020
publisher MDPI
record_format MEDLINE/PubMed
spelling pubmed-77619082020-12-26 Recyclable Organocatalyzed Poly(Thiourethane) Covalent Adaptable Networks Gamardella, Francesco Muñoz, Sara De la Flor, Silvia Ramis, Xavier Serra, Angels Polymers (Basel) Article A new type of tetraphenylborate salts derived from highly basic and nucleophilic amines, namely 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU) and triazabicyclodecene (TBD), was applied to the preparation of networked poly(thiourethane)s (PTUs), which showed a vitrimer-like behavior, with higher stress-relaxation rates than PTUs prepared by using dibutyl thin dilaurate (DBTDL) as the catalyst. The use of these salts, which release the amines when heated, instead of the pure amines, allows the formulation to be easily manipulated to prepare any type of samples. The materials prepared from stoichiometric mixtures of hexamethylene diisocyanate (HDI), trithiol (S3) and with a 10% of molar excess of isocyanate or thiol were characterized by FTIR, thermomechanical analysis, thermogravimetry, stress-relaxation tests and tensile tests, thus obtaining a complete thermal and mechanical characterization of the materials. The recycled materials obtained by grinding the original PTUs and hot-pressing the small pieces in the optimized time and temperature conditions were fully characterized by mechanical, thermomechanical and FTIR studies. This allowed us to confirm their recyclability, without appreciable changes in the network structure and performance. From several observations, the dissociative interchange trans-thiocarbamoylation mechanism was evidenced as the main responsible of the topological rearrangements at high temperature, resulting in a vitrimeric-like behavior. MDPI 2020-12-04 /pmc/articles/PMC7761908/ /pubmed/33291704 http://dx.doi.org/10.3390/polym12122913 Text en © 2020 by the authors. 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 (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Gamardella, Francesco
Muñoz, Sara
De la Flor, Silvia
Ramis, Xavier
Serra, Angels
Recyclable Organocatalyzed Poly(Thiourethane) Covalent Adaptable Networks
title Recyclable Organocatalyzed Poly(Thiourethane) Covalent Adaptable Networks
title_full Recyclable Organocatalyzed Poly(Thiourethane) Covalent Adaptable Networks
title_fullStr Recyclable Organocatalyzed Poly(Thiourethane) Covalent Adaptable Networks
title_full_unstemmed Recyclable Organocatalyzed Poly(Thiourethane) Covalent Adaptable Networks
title_short Recyclable Organocatalyzed Poly(Thiourethane) Covalent Adaptable Networks
title_sort recyclable organocatalyzed poly(thiourethane) covalent adaptable networks
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7761908/
https://www.ncbi.nlm.nih.gov/pubmed/33291704
http://dx.doi.org/10.3390/polym12122913
work_keys_str_mv AT gamardellafrancesco recyclableorganocatalyzedpolythiourethanecovalentadaptablenetworks
AT munozsara recyclableorganocatalyzedpolythiourethanecovalentadaptablenetworks
AT delaflorsilvia recyclableorganocatalyzedpolythiourethanecovalentadaptablenetworks
AT ramisxavier recyclableorganocatalyzedpolythiourethanecovalentadaptablenetworks
AT serraangels recyclableorganocatalyzedpolythiourethanecovalentadaptablenetworks