title: Synthesis of three different galactose-based methacrylate monomers for the production of sugar-based polymers.
abstract: Glycopolymers, synthetic sugar-containing macromolecules, are attracting ever-increasing interest from the chemistry community. Glycidyl methacrylate (GMA) is an important building block for the synthesis of sugar based methacrylate monomers and polymers. Normally, glycidyl methacrylate shows some advantages such as reactivity against nucleophiles or milder synthetic conditions such as other reactive methacrylate monomers. However, condensation reactions of glycidyl methacrylate with for instance protected galactose monomer leads to a mixture of two products due to a strong competition between the two possible pathways: epoxide ring opening or transesterification. In this paper, we propose two alternative routes to synthesize regiospecific galactose-based methacrylate monomers using the epoxy-ring opening reaction. In the first alternative route, the protected galactose is first oxidized to the acid in order to make it more reactive against the epoxide of GMA. In the second route, the protected sugar was first treated with epichlorohydrin followed by the epoxy ring opening reaction with methacrylic acid, to create an identical analogue of the ring-opening product of GMA. These two monomers were polymerized using conventional radical polymerization and were compared to the previously known galactose-methacrylate one. The new polymers show similar thermal stability but lower glass transition temperature (Tg) with respect to the known galactose methacrylate polymer.
authors.affiliation: POLYMAT, University of the Basque Country UPV/EHU, Joxe Mari Korta Center, 20018, Donostia-San Sebastián, Spain.
authors.forename: Jessica S
authors.initials: JS
authors.lastname: Desport
authors.affiliation: POLYMAT, University of the Basque Country UPV/EHU, Joxe Mari Korta Center, 20018, Donostia-San Sebastián, Spain.
authors.forename: Daniele
authors.initials: D
authors.lastname: Mantione
authors.affiliation: POLYMAT, University of the Basque Country UPV/EHU, Joxe Mari Korta Center, 20018, Donostia-San Sebastián, Spain.
authors.forename: Mónica
authors.initials: M
authors.lastname: Moreno
authors.affiliation: POLYMAT, University of the Basque Country UPV/EHU, Joxe Mari Korta Center, 20018, Donostia-San Sebastián, Spain.
authors.forename: Haritz
authors.initials: H
authors.lastname: Sardón
authors.affiliation: POLYMAT, University of the Basque Country UPV/EHU, Joxe Mari Korta Center, 20018, Donostia-San Sebastián, Spain.
authors.forename: María J
authors.initials: MJ
authors.lastname: Barandiaran
authors.affiliation: POLYMAT, University of the Basque Country UPV/EHU, Joxe Mari Korta Center, 20018, Donostia-San Sebastián, Spain; Ikerbasque, Basque Foundation for Science, E-48011, Bilbao, Spain. Electronic address: daniele.mantione@ehu.es.
authors.forename: David
authors.initials: D
authors.lastname: Mecerreyes
mesh_terms: D005690:Galactose / Q000737:chemistry*; D046911:Macromolecular Substances / Q000138:chemical synthesis / Q000737:chemistry; D008422:Materials Testing; D008689:Methacrylates / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D058105:Polymerization; D011108:Polymers / Q000138:chemical synthesis / Q000737:chemistry; D013499:Surface Properties
chemical_list: D046911:Macromolecular Substances; D008689:Methacrylates; D011108:Polymers; D005690:Galactose
keywords: AMC-2 catalyst; Epoxide ring opening; Free radical polymerization; Glycidyl methacrylate (GMA); Isopropylidene-D-galactopyranose