Straightforward Enzymatic Methacrylation of Poly(Glycerol Adipate) for Potential Applications as UV Curing Systems
Enzymatic one-pot synthesis procedures in a one-step and two-step monomers addition were developed to obtain poly(glycerol adipate) macromers with methacrylate end-functional groups under the presence of 1 and 3 wt% of <i>Candida antarctica</i> lipase B (CALB). Glycerol, divinyl adipate,...
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| Format: | Article |
| Language: | English |
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MDPI AG
2023-07-01
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| Series: | Polymers |
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| Online Access: | https://www.mdpi.com/2073-4360/15/14/3050 |
| _version_ | 1797587667388465152 |
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| author | Víctor Hevilla Águeda Sonseca Marta Fernández-García |
| author_facet | Víctor Hevilla Águeda Sonseca Marta Fernández-García |
| author_sort | Víctor Hevilla |
| collection | DOAJ |
| description | Enzymatic one-pot synthesis procedures in a one-step and two-step monomers addition were developed to obtain poly(glycerol adipate) macromers with methacrylate end-functional groups under the presence of 1 and 3 wt% of <i>Candida antarctica</i> lipase B (CALB). Glycerol, divinyl adipate, and vinyl methacrylate were enzymatically reacted (vinyl methacrylate was either present from the beginning in the monomers solution or slowly dropped after 6 h of reaction) in tetrahydrofuran (THF) at 40 °C over 48 h. Macromers with a methacrylate end groups fraction of ≈52% in a simple one-pot one-step procedure were obtained with molecular weights (M<sub>n</sub>) of ≈7500–7900 g/mol. The obtained products under the one-pot one-step and two steps synthesis procedures carried out using 1 and 3 wt% of a CALB enzymatic catalyst were profusely characterized by NMR (<sup>1</sup>H and <sup>13</sup>C), MALDI-TOF MS, and SEC. The methacrylate functional macromers obtained with the different procedures and 1 wt% of CALB were combined with an Irgacure<sup>®</sup> 369 initiator to undergo homopolymerization under UV irradiation for 10 and 30 min, in order to test their potential to obtain amorphous networks within minutes with similar properties to those typically obtained by complex acrylation/methacrylation procedures, which need multiple purification steps and harsh reagents such as acyl chlorides. To the best of our knowledge, this is the first time that it has been demonstrated that the obtention of methacrylate-functional predominantly linear macromers based on poly(glycerol adipate) is able to be UV crosslinked in a simple one-step procedure. |
| first_indexed | 2024-03-11T00:43:04Z |
| format | Article |
| id | doaj.art-8755f9a1eead4946b2ac930c8d562d62 |
| institution | Directory Open Access Journal |
| issn | 2073-4360 |
| language | English |
| last_indexed | 2024-03-11T00:43:04Z |
| publishDate | 2023-07-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Polymers |
| spelling | doaj.art-8755f9a1eead4946b2ac930c8d562d622023-11-18T21:02:36ZengMDPI AGPolymers2073-43602023-07-011514305010.3390/polym15143050Straightforward Enzymatic Methacrylation of Poly(Glycerol Adipate) for Potential Applications as UV Curing SystemsVíctor Hevilla0Águeda Sonseca1Marta Fernández-García2Instituto de Ciencia y Tecnología de Polímeros (ICTP-CSIC), C/Juan de la Cierva, 3, 28006 Madrid, SpainInstituto de Tecnología de Materiales, Universitat Politècnica de València, Camino de Vera, s/n, 46022 Valencia, SpainInstituto de Ciencia y Tecnología de Polímeros (ICTP-CSIC), C/Juan de la Cierva, 3, 28006 Madrid, SpainEnzymatic one-pot synthesis procedures in a one-step and two-step monomers addition were developed to obtain poly(glycerol adipate) macromers with methacrylate end-functional groups under the presence of 1 and 3 wt% of <i>Candida antarctica</i> lipase B (CALB). Glycerol, divinyl adipate, and vinyl methacrylate were enzymatically reacted (vinyl methacrylate was either present from the beginning in the monomers solution or slowly dropped after 6 h of reaction) in tetrahydrofuran (THF) at 40 °C over 48 h. Macromers with a methacrylate end groups fraction of ≈52% in a simple one-pot one-step procedure were obtained with molecular weights (M<sub>n</sub>) of ≈7500–7900 g/mol. The obtained products under the one-pot one-step and two steps synthesis procedures carried out using 1 and 3 wt% of a CALB enzymatic catalyst were profusely characterized by NMR (<sup>1</sup>H and <sup>13</sup>C), MALDI-TOF MS, and SEC. The methacrylate functional macromers obtained with the different procedures and 1 wt% of CALB were combined with an Irgacure<sup>®</sup> 369 initiator to undergo homopolymerization under UV irradiation for 10 and 30 min, in order to test their potential to obtain amorphous networks within minutes with similar properties to those typically obtained by complex acrylation/methacrylation procedures, which need multiple purification steps and harsh reagents such as acyl chlorides. To the best of our knowledge, this is the first time that it has been demonstrated that the obtention of methacrylate-functional predominantly linear macromers based on poly(glycerol adipate) is able to be UV crosslinked in a simple one-step procedure.https://www.mdpi.com/2073-4360/15/14/3050poly(glycerol adipate)enzymatic synthesisfunctionalizationstepsUV-curing |
| spellingShingle | Víctor Hevilla Águeda Sonseca Marta Fernández-García Straightforward Enzymatic Methacrylation of Poly(Glycerol Adipate) for Potential Applications as UV Curing Systems Polymers poly(glycerol adipate) enzymatic synthesis functionalization steps UV-curing |
| title | Straightforward Enzymatic Methacrylation of Poly(Glycerol Adipate) for Potential Applications as UV Curing Systems |
| title_full | Straightforward Enzymatic Methacrylation of Poly(Glycerol Adipate) for Potential Applications as UV Curing Systems |
| title_fullStr | Straightforward Enzymatic Methacrylation of Poly(Glycerol Adipate) for Potential Applications as UV Curing Systems |
| title_full_unstemmed | Straightforward Enzymatic Methacrylation of Poly(Glycerol Adipate) for Potential Applications as UV Curing Systems |
| title_short | Straightforward Enzymatic Methacrylation of Poly(Glycerol Adipate) for Potential Applications as UV Curing Systems |
| title_sort | straightforward enzymatic methacrylation of poly glycerol adipate for potential applications as uv curing systems |
| topic | poly(glycerol adipate) enzymatic synthesis functionalization steps UV-curing |
| url | https://www.mdpi.com/2073-4360/15/14/3050 |
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