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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 (Me 6 TREN) 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 < Đ < 1.16). Interestingly, poly(THFLA) showed a degree of polymerization and concentration dependent LCST behavior, which can be fine-tuned ( T cp = 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. 

Depending on the order of addition to the reaction mixture during biphasic SET-LRP performed in acetone/water mixtures, acetone can serve as a solvent or as a reagent brominated by CuBr 2 to provide the electrophilic bromoacetone initiator as well as aldol condensation products.