A green solvent-to-polymer upgrading approach to water-soluble LCST poly(N-substituted lactamide acrylate)s

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-substi...

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Bibliographic Details
Main Authors: Palà, Marc, El Khannaji, Hafssa, Garay-Sarmiento, Manuela, Ronda, Juan Carlos, Cádiz, Virginia, Galià, Marina, Percec, Virgil, Rodriguez-Emmenegger, César, Lligadas, Gerard
Format: Article in Journal/Newspaper
Language:English
Published: Cambridge : RSC 2022
Subjects:
Acrylic monomers
Biocompatibility
Copolymerization
Crosslinking
Lactic acid
Living polymerization
Solvents
Substitution reactions
Swelling
Acrylic co-polymers
Acrylic polymers
Condition
Critical solution temperature
Greener solvents
Living radical polymerization
Lower critical
Rapid synthesis
SET-LRP
Watersoluble
Copper compounds
ddc:540
DML
Online Access:https://oa.tib.eu/renate/handle/123456789/10788
https://doi.org/10.34657/9814
Description
Summary: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® 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 < Mn < 83 000) and dispersity (1.05 < Đ < 1.16). Interestingly, poly(THFLA) showed a degree of polymerization and concentration dependent LCST behavior, which can be fine-tuned (Tcp = 12–62 °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.

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