Preparation of poly(thiourethane) networks by using a novel acidic organocatalyst. Evaluation of their vitrimer-like behavior

Guerrero, Federico; Ramis, Xavier; Flor, Silvia De la; Serra, À.

doi:10.1016/j.reactfunctpolym.2023.105501

Cited by 10 publications

(10 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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“…In previous studies, our group demonstrated the vitrimer-like characteristics of poly(thiourethane) networks [ 7 , 8 , 10 , 11 , 12 ]. The interchange reaction responsible for the vitrimer-like behavior is the transthiocarbamoylation reaction.…”

Section: Resultsmentioning

confidence: 99%

“…Our group has deeply studied the vitrimer-like characteristics of poly(thiourethane) (PTU) networks [ 7 , 8 , 9 , 10 , 11 , 12 ]. These materials have excellent optical properties and can easily be reshaped and recycled [ 13 , 14 ].…”

Section: Introductionmentioning

confidence: 99%

Preparation and Characterization of a Series of Self-Healable Bio-Based Poly(thiourethane) Vitrimer-like Materials

et al. 2023

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A series of poly(thiourethanes) (PTUs) from biobased monomers have been synthesized. Limonene and squalene were transformed into polyfunctional thiols by thiol-ene reaction with thioacetic acid and further saponification. They were then reacted in different proportions with hexamethylene diisocyanate (HDI) in the presence of a catalyst to prepare bio-based poly(thiourethane) vitrimer-like materials. The different functionalities of squalene and limonene thiols (six and two, respectively) allow for changing the characteristics of the final material by only varying their relative proportions in the reactive mixture. The proportions of thiol and isocyanate groups were stoichiometric in all the formulations tested. An acidic and a basic catalyst were tested in the preparation of the networked polymers. As the acidic catalyst, we selected dibutyltin dilaurate (DBTDL), and as the basic catalyst, a tetraphenylborate salt of 1,8-diazabicyclo(5.4.0)undec-7-ene (BGDBU), which has the advantage of only releasing the base at high temperatures. The materials obtained were characterized by thermogravimetry and thermomechanical analysis. The vitrimeric-like behavior was evaluated, and we could see that higher proportions of the limonene derivative in the formulations led to faster stress relaxation of the material. The use of the base catalyst led to a much shorter relaxation time. The materials obtained demonstrated good self-healing efficiency.

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“…This activation can be triggered by several stimuli, including heat and light. [10][11][12][13][14][15][16][17][18][19][20] It should be facile and cost-effective to prepare and demonstrate a high level of reactivity after activation. Latent catalysts have been employed in CANs, allowing for precise manipulation of exchange reactions.…”

Section: Introductionmentioning

confidence: 99%

Latent catalysts in vitrimers

Nikita,

Kumar,

Connal

2024

Polym. Chem.

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Preparation of poly(thiourethane) networks by using a novel acidic organocatalyst. Evaluation of their vitrimer-like behavior

Cited by 10 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 a Series of Self-Healable Bio-Based Poly(thiourethane) Vitrimer-like Materials

Latent catalysts in vitrimers

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