Preparation and Characterization of a Series of Self-Healable Bio-Based Poly(thiourethane) Vitrimer-like Materials
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 diisocyanat...
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| Format: | Article |
| Language: | English |
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MDPI AG
2023-03-01
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| Series: | Polymers |
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| Online Access: | https://www.mdpi.com/2073-4360/15/6/1583 |
| _version_ | 1797609264302260224 |
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| author | Federico Guerrero Xavier Ramis Silvia De la Flor Àngels Serra |
| author_facet | Federico Guerrero Xavier Ramis Silvia De la Flor Àngels Serra |
| author_sort | Federico Guerrero |
| collection | DOAJ |
| description | 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. |
| first_indexed | 2024-03-11T05:59:03Z |
| format | Article |
| id | doaj.art-3f337c28f9da4766bb045e6a1675ea32 |
| institution | Directory Open Access Journal |
| issn | 2073-4360 |
| language | English |
| last_indexed | 2024-03-11T05:59:03Z |
| publishDate | 2023-03-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Polymers |
| spelling | doaj.art-3f337c28f9da4766bb045e6a1675ea322023-11-17T13:27:34ZengMDPI AGPolymers2073-43602023-03-01156158310.3390/polym15061583Preparation and Characterization of a Series of Self-Healable Bio-Based Poly(thiourethane) Vitrimer-like MaterialsFederico Guerrero0Xavier Ramis1Silvia De la Flor2Àngels Serra3Analytical and Organic Chemistry Department, Universitat Rovira i Virgili, C/ Marcel·lí Domingo s/n Edificio N4, 43007 Tarragona, SpainThermodynamics Laboratory, Universitat Politècnica de Catalunya ETSEIB, Av. Diagonal 647, 08028 Barcelona, SpainDepartment of Mechanical Engineering, Universitat Rovira i Virgili, Av. Països Catalans, 26, 43007 Tarragona, SpainAnalytical and Organic Chemistry Department, Universitat Rovira i Virgili, C/ Marcel·lí Domingo s/n Edificio N4, 43007 Tarragona, SpainA 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.https://www.mdpi.com/2073-4360/15/6/1583poly(thiourethanes)thiolvitrimersrenewablebio-based monomers |
| spellingShingle | Federico Guerrero Xavier Ramis Silvia De la Flor Àngels Serra Preparation and Characterization of a Series of Self-Healable Bio-Based Poly(thiourethane) Vitrimer-like Materials Polymers poly(thiourethanes) thiol vitrimers renewable bio-based monomers |
| title | Preparation and Characterization of a Series of Self-Healable Bio-Based Poly(thiourethane) Vitrimer-like Materials |
| title_full | Preparation and Characterization of a Series of Self-Healable Bio-Based Poly(thiourethane) Vitrimer-like Materials |
| title_fullStr | Preparation and Characterization of a Series of Self-Healable Bio-Based Poly(thiourethane) Vitrimer-like Materials |
| title_full_unstemmed | Preparation and Characterization of a Series of Self-Healable Bio-Based Poly(thiourethane) Vitrimer-like Materials |
| title_short | Preparation and Characterization of a Series of Self-Healable Bio-Based Poly(thiourethane) Vitrimer-like Materials |
| title_sort | preparation and characterization of a series of self healable bio based poly thiourethane vitrimer like materials |
| topic | poly(thiourethanes) thiol vitrimers renewable bio-based monomers |
| url | https://www.mdpi.com/2073-4360/15/6/1583 |
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