Author, as appears in the article.: Pala, Marc; El Khannaji, Hafssa; Garay-Sarmiento, Manuela; Carlos Ronda, Juan; Cadiz, Virginia; Galia, Marina; Percec, Virgil; Rodriguez-Emmenegger, Cesar; Lligadas, Gerard;
Department: Química Analítica i Química Orgànica
URV's Author/s: Cádiz Deleito, Maria Virginia / Galià Clua, Marina Teresa / Lligadas Puig, Gerard / PALÀ SÁNCHEZ, MARC / Ronda Bargalló, Juan Carlos
Keywords: Thermoresponsive polymers Single Set-lrp Ruthenium nanoparticles Reductive amination Pnipam Monomers Living radical polymerization Ethyl lactate Acid
Abstract: We report a green solvent-to-polymer upgrading transformation of chemicals of the lactic acid portfolio into water-soluble lower critical solution temperature (LCST)-type acrylic polymers. Aqueous Cu(0)-mediated living radical polymerization (SET-LRP) was utilized for the rapid synthesis of N-substituted lactamide-type homo and random acrylic copolymers under mild conditions. A particularly unique aspect of this work is that the water-soluble monomers and the SET-LRP initiator used to produce the corresponding polymers were synthesized from biorenewable and non-toxic solvents, namely natural ethyl lactate and BASF's Agnique (R) AMD 3L (N,N-dimethyl lactamide, DML). The pre-disproportionation of Cu(I) Br in the presence of tris[2-(dimethylamino)ethyl]amine (Me6TREN) in water generated nascent Cu(0) and Cu(II) complexes that facilitated the fast polymerization of N-tetrahydrofurfuryl lactamide and N,N-dimethyl lactamide acrylate monomers (THFLA and DMLA, respectively) up to near-quantitative conversion with excellent control over molecular weight (5000 < M-n < 83 000) and dispersity (1.05 < D < 1.16). Interestingly, poly(THFLA) showed a degree of polymerization and concentration dependent LCST behavior, which can be fine-tuned (T-cp = 12-62 degrees C) through random copolymerization with the more hydrophilic DMLA monomer. Finally, covalent cross-linking of these polymers resulted in a new family of thermo-responsive hydrogels with excellent biocompatibility and tunable swelling and LCST transition. These illustrate the versatility of these neoteric green polymers in the preparation of smart and biocompatible soft materials.
Thematic Areas: Química Pollution Medicina veterinaria Medicina ii Materiais Interdisciplinar Green & sustainable science & technology Farmacia Environmental chemistry Engenharias iv Engenharias iii Engenharias ii Ciências biológicas ii Ciências biológicas i Ciências agrárias i Ciência de alimentos Chemistry, multidisciplinary Chemistry Biotecnología Astronomia / física
licence for use: https://creativecommons.org/licenses/by/3.0/es/
Author's mail: marc.pala@urv.cat marc.pala@urv.cat marina.galia@urv.cat juancarlos.ronda@urv.cat gerard.lligadas@urv.cat
Author identifier: 0000-0002-4359-4510 0000-0002-0668-6600 0000-0002-8519-1840
Record's date: 2024-09-07
Papper version: info:eu-repo/semantics/publishedVersion
Link to the original source: https://pubs.rsc.org/en/content/articlelanding/2022/gc/d2gc02780a
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Papper original source: Green Chemistry. 24 (21): 8314-8323
APA: Pala, Marc; El Khannaji, Hafssa; Garay-Sarmiento, Manuela; Carlos Ronda, Juan; Cadiz, Virginia; Galia, Marina; Percec, Virgil; Rodriguez-Emmenegger, C (2022). A green solvent-to-polymer upgrading approach to water-soluble LCST poly(N-substituted lactamide acrylate)s. Green Chemistry, 24(21), 8314-8323. DOI: 10.1039/d2gc02780a
Article's DOI: 10.1039/d2gc02780a
Entity: Universitat Rovira i Virgili
Journal publication year: 2022
Publication Type: Journal Publications
Repositori URV