Journal
GREEN CHEMISTRY
Volume 24, Issue 21, Pages 8314-8323Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d2gc02780a
Keywords
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Funding
- Serra Hunter Programme of the Government of Catalonia
- Univesitat Rovira i Virgili [2020-PMF-PIPF-41]
- FPI [PRE2021100387]
- MCIN/AEI [PID2020-114098RB-100]
- German Federal Ministry of Education and Research (BMBF)
- project AntiBacCat and Heart2.0 within the Bio4MatPro-Competence Center for Biological Transformation of Materials Science and Production Engineering program [031B1153A, 031B1154B]
- National Science Foundation [DMR-1807127, DMR-1720530, DMR-2104554]
- Humboldt Foundation
- P. Roy Vagelos Chair at Penn
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This research reports a green method for upgrading chemicals of the lactic acid portfolio into water-soluble acrylic polymers, utilizing lactate-derived solvents and Cu(0)-mediated living radical polymerization. The resulting polymers exhibit excellent biocompatibility and thermal responsiveness, forming a new family of hydrogels.
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.
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