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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ftleibnizopen:oai:oai.leibnizopen.de:J-QqsIYBdbrxVwz6bXEf 2023-05-15T16:02:05+02:00 A green solvent-to-polymer upgrading approach to water-soluble LCST poly(N-substituted lactamide acrylate)s Palà, Marc El Khannaji, Hafssa Garay-Sarmiento, Manuela Ronda, Juan Carlos Cádiz, Virginia Galià, Marina Percec, Virgil Rodriguez-Emmenegger, César Lligadas, Gerard 2022 application/pdf https://oa.tib.eu/renate/handle/123456789/10788 https://doi.org/10.34657/9814 eng eng Cambridge : RSC CC BY 3.0 Unported https://creativecommons.org/licenses/by/3.0/ CC-BY Green chemistry : GC 24 (2022), Nr. 21 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 540 article Text 2022 ftleibnizopen https://doi.org/10.34657/9814 2023-03-06T00:14:52Z 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. publishedVersion Article in Journal/Newspaper DML LeibnizOpen (The Leibniz Association) |
institution |
Open Polar |
collection |
LeibnizOpen (The Leibniz Association) |
op_collection_id |
ftleibnizopen |
language |
English |
topic |
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 540 |
spellingShingle |
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 540 Palà, Marc El Khannaji, Hafssa Garay-Sarmiento, Manuela Ronda, Juan Carlos Cádiz, Virginia Galià, Marina Percec, Virgil Rodriguez-Emmenegger, César Lligadas, Gerard A green solvent-to-polymer upgrading approach to water-soluble LCST poly(N-substituted lactamide acrylate)s |
topic_facet |
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 540 |
description |
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. publishedVersion |
format |
Article in Journal/Newspaper |
author |
Palà, Marc El Khannaji, Hafssa Garay-Sarmiento, Manuela Ronda, Juan Carlos Cádiz, Virginia Galià, Marina Percec, Virgil Rodriguez-Emmenegger, César Lligadas, Gerard |
author_facet |
Palà, Marc El Khannaji, Hafssa Garay-Sarmiento, Manuela Ronda, Juan Carlos Cádiz, Virginia Galià, Marina Percec, Virgil Rodriguez-Emmenegger, César Lligadas, Gerard |
author_sort |
Palà, Marc |
title |
A green solvent-to-polymer upgrading approach to water-soluble LCST poly(N-substituted lactamide acrylate)s |
title_short |
A green solvent-to-polymer upgrading approach to water-soluble LCST poly(N-substituted lactamide acrylate)s |
title_full |
A green solvent-to-polymer upgrading approach to water-soluble LCST poly(N-substituted lactamide acrylate)s |
title_fullStr |
A green solvent-to-polymer upgrading approach to water-soluble LCST poly(N-substituted lactamide acrylate)s |
title_full_unstemmed |
A green solvent-to-polymer upgrading approach to water-soluble LCST poly(N-substituted lactamide acrylate)s |
title_sort |
green solvent-to-polymer upgrading approach to water-soluble lcst poly(n-substituted lactamide acrylate)s |
publisher |
Cambridge : RSC |
publishDate |
2022 |
url |
https://oa.tib.eu/renate/handle/123456789/10788 https://doi.org/10.34657/9814 |
genre |
DML |
genre_facet |
DML |
op_source |
Green chemistry : GC 24 (2022), Nr. 21 |
op_rights |
CC BY 3.0 Unported https://creativecommons.org/licenses/by/3.0/ |
op_rightsnorm |
CC-BY |
op_doi |
https://doi.org/10.34657/9814 |
_version_ |
1766397704525578240 |