The use of lanthanide triflates in the preparation of poly(thiourethane) covalent adaptable networks

Guerrero, Federico; Gamardella, Francesco; Ramis, Xavier; Flor, Silvia De la; Serra, Àngels

doi:10.1016/j.polymer.2023.126262

Cited by 4 publications

(2 citation statements)

References 33 publications

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“…Over the past few years, Serra and co-workers − ,, have shown that these materials exhibit vitrimeric-like behavior, characterized by the dissociation of the thiourethane group into isocyanate and thiol. This process is followed by rapid reformation, resulting in a decrease in viscosity upon heating, following an Arrhenius-type evolution.…”

Section: Resultsmentioning

confidence: 99%

“…PTUs are synthesized through the condensation of isocyanates and thiols, resulting in materials with dynamic properties facilitated by thiourethane–thiourethane or thiol–thiourethane exchange reactions . Since the initial report in 2019 by Torkelson’s group, various thiol–isocyanate systems with dynamic properties have been investigated, employing different catalysts and exploring sustainable alternatives. − In the quest for more sustainable materials, there have been reports on substituting monomers derived from biomass for those derived from fossils, along with the development of non-isocyanate poly(thiourethane)s (NIPTUs). , Additionally, dynamic PTUs have been employed as a polymeric matrix in nanocomposites …”

Section: Introductionmentioning

confidence: 99%

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Revealing Dynamic Behavior in High Dielectric Poly(thiourethane)-Based Vitrimer-like Materials

Guerrero-Ruiz,

Otaegi,

Verde-Sesto

et al. 2024

ACS Appl. Polym. Mater.

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Here, we have explored covalent adaptable networks (CANs) comprising poly(thiourethane)-based systems (PTUs). The PTUs were synthesized through the combination of thiol and isocyanate monomers in stoichiometric proportions, in the presence of dibutyltin dilaurate (DBTDL) as catalyst. Dynamic mechanical analysis (DMA) provided detailed insight into the vitrimeric behavior. Through these investigations, we evaluated the viscoelastic, thermomechanical, and vitrimeric properties. Additionally, broadband dielectric spectroscopy (BDS) revealed the various relaxation processes inherent in such vitrimer-like materials. We methodically examined the evolution of each relaxation in every prepared sample to comprehend the operational mechanisms in these vitrimer-like systems. Our findings underscore that depending on the PTU formulation, the glass transition temperature (T g) and the topology freezing transition temperature (T v) can be effectively distinguished and studied. Considering the high dipole moment of the dynamic bonds present in these systems, there is potential for utilizing them as dielectric materials working under the concept of dipolar glass polymers. Furthermore, the reversibility exhibited by their inner chemical structures positions them as promising candidates for active layers in capacitor devices, particularly for energy-related applications, with the ability to be recyclable while maintaining almost invariant both their mechanical and dielectric properties, thus promoting the extension of the lifespan of electronic devices.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Revealing Dynamic Behavior in High Dielectric Poly(thiourethane)-Based Vitrimer-like Materials

Guerrero-Ruiz,

Otaegi,

Verde-Sesto

et al. 2024

ACS Appl. Polym. Mater.

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Preparation and Characterization of Novel Poly(thiourethane)–Poly(isocyanurate) Covalent Adaptable Networks: Effect of the Catalysts

Guerrero,

De la Flor,

Serra

2024

Macromol. Rapid Commun.

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Poly(thiourethane)‐based covalent adaptable networks are synthesized by reacting a trimer of hexamethylene diisocyanate (Desmodur N3300) containing isocyanurate groups in its structure with 1,6‐hexanedithiol. The catalysts evaluated for this process include dibutyltin dilaurate (DBTDL), lanthanum triflate (La(OTf)3), and a thermal precursor of 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (BGDBU). The use of DBTDL results in the initiation of curing upon mixing, while the other two catalysts exhibit a latency period in the reactive mixture, with curing starting at about 90 °C. Notably, the use of the lanthanum salt produces an additional minor exothermic reaction at 80 °C. This phenomenon corresponds to the trimerization of isocyanates rending isocyanurates, leaving a portion of unreacted thiols. Materials prepared with BGDBU or La(OTf)3 present shorter relaxation times than those prepared with DBTDL. Nevertheless, the materials containing the lanthanum salt do not reach complete relaxation, likely due to the reinforcement of the permanent network through increased isocyanurate content. The formation of isocyanurates produces a stoichiometric imbalance, leaving unreacted thiols. This transforms the exchange process into a dual mechanism involving a dissociative process of thiourethanes to isocyanate and thiol, along with an interchange through thiol attacking the thiourethane group. The materials exhibit good recyclability and self‐healing characteristics.

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Probing the remarkable vitrimeric performance of Poly(dithiourethanes): A comprehensive investigation into the dynamic behavior

Guerrero-Ruiz,

Bonardd,

Otaegi

et al. 2024

European Polymer Journal

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The use of lanthanide triflates in the preparation of poly(thiourethane) covalent adaptable networks

Cited by 4 publications

References 33 publications

Revealing Dynamic Behavior in High Dielectric Poly(thiourethane)-Based Vitrimer-like Materials

Revealing Dynamic Behavior in High Dielectric Poly(thiourethane)-Based Vitrimer-like Materials

Preparation and Characterization of Novel Poly(thiourethane)–Poly(isocyanurate) Covalent Adaptable Networks: Effect of the Catalysts

Probing the remarkable vitrimeric performance of Poly(dithiourethanes): A comprehensive investigation into the dynamic behavior

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