title: High Glass Transition Temperature Renewable Polymers via Biginelli Multicomponent Polymerization.
abstract: A novel and straightforward one-pot multicomponent polycondensation method was established in this work. The Biginelli reaction is a versatile multicomponent reaction of an aldehyde, a β-ketoester (acetoacetate) and urea, which can all be obtained from renewable resources, yielding diversely substituted 3,4-dihydropyrimidin-2(1H)-ones (DHMPs). In this study, renewable diacetoacetate monomers with different spacer chain lengths (C3, C6, C10, C20) were prepared via simple transesterification of renewable diols and commercial acetoacetates. The diacetoacetate monomers were then reacted with renewable dialdehydes, i.e., terephthalaldehyde and divanillin in a Biginelli type step-growth polymerization. The obtained DHMP polymers (polyDHMPs) displayed high molar masses, high glass transition temperatures (Tg) up to 203 °C and good thermal stability (Td5%) of 280 °C. The Tg of the polyDHMPs could be tuned by variation of the structure of the dialdehyde or the diacetoacetate component.
authors.affiliation: Laboratory of Applied Chemistry, Institute of Organic Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, Karlsruhe, 76131, Germany.
authors.forename: Andreas C
authors.initials: AC
authors.lastname: Boukis
authors.affiliation: Laboratory of Applied Chemistry, Institute of Organic Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, Karlsruhe, 76131, Germany.
authors.forename: Audrey
authors.initials: A
authors.lastname: Llevot
authors.affiliation: Laboratory of Applied Chemistry, Institute of Organic Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, Karlsruhe, 76131, Germany.
authors.forename: Michael A R
authors.initials: MA
authors.lastname: Meier
mesh_terms: D000090:Acetoacetates / Q000737:chemistry; D000438:Alcohols / Q000737:chemistry; D000447:Aldehydes / Q000737:chemistry; D002152:Calorimetry, Differential Scanning; D002384:Catalysis; D058105:Polymerization; D011108:Polymers / Q000138:chemical synthesis / Q000737:chemistry*; D044366:Transition Temperature; D014508:Urea / Q000737:chemistry
chemical_list: D000090:Acetoacetates; D000438:Alcohols; D000447:Aldehydes; D011108:Polymers; C016635:acetoacetic acid; D014508:Urea
keywords: Biginelli reaction; glass transition; multicomponent reactions; renewable resources; step-growth polymerization