Polímeros: Ciência e Tecnologia
https://revistapolimeros.org.br/article/doi/10.1590/0104-1428.20250043
Polímeros: Ciência e Tecnologia
Original Article

Modulating molecular weight and crosslinking in thiol-ene polymerization of renewable monomer limonene

Luiz Paulo Soares Pereira; Marina de Souza Melchiors; Thayne Yasmin Vieira; Tamara Agner; Bruno Augusto Mattar Carciofi; Pedro Henrique Hermes de Araújo; Débora de Oliveira; Claudia Sayer

http://dx.doi.org/10.1590/0104-1428.20250043 Polímeros: Ciência e Tecnologia, vol.35, n4, e20250044, 2025
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Abstract

Limonene, a renewable material derived from citrus fruit peels, can be used as monomer in thiol-ene polymerization with dithiols and tetrathiols to form linear or crosslinked polymers, respectively. The effect of using a thermal- or photoinitiator on polymer properties was evaluated, with the photoinitiator significantly increasing the conversion of the internal unsaturation of limonene with 1,4-butanedithiol (>90%), resulting in higher molecular weights (9,000 g/mol). With pentaerythritiol tetrakis(3-mercaptopropionate), the gel content remained below 15% in thermally initiated reactions (28,000 g/mol) but increased to above 90% in photoinitiated ones. Finally, combining both thiols resulted in an intermediate molecular weight (~13,000 g/mol) for thermal initiation, and a gel content of about 85% for the photoinitiated ones. Thus, thiol-ene reactions stand out as an effective approach for the synthesis of polymers from limonene, with molecular weight and gel content being fine-tuned by the type/ amount of initiator, and by the combination of di- and tetrathiol.

 

 

Keywords

green chemistry, photopolymerization, renewable monomers, thiol-ene polymerization

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