Synthesis of biorenewable and water-degradable polylactam esters from itaconic acid

Abstract

Itaconic acid, a naturally occurring compound mass-produced via fermentation of glucose, was reacted with ethanolamine or ethylene diamine to afford hydroxy-acid or diacid monomers containing the 2-pyrrolidone lactam. Homopolymerization or copolymerization with diols, respectively, yielded polylactam esters with higher glass transition temperatures and faster hydrolytic degradation compared to the commercial polyester polylactic acid (PLA).

Renewable (Bis)pyrrolidone Based Monomers as Components for Thermally Curable and Enzymatically Depolymerizable 2-Oxazoline Thermoset Resins

“… 2 , 3 2,5-Furandicarboxylic acid, generally obtained from hydroxymethyl furfural or its derivatives, 4 has proven to exhibit excellent gas permeability properties in thermoplastic materials 5 and has also proven applicable for thermosetting resins. 6 Itaconic acid, having two carboxylic functionalities combined with the presence of a vinyl group, has proven to be of interest for the synthesis of renewable polyesters, 7 − 11 polyester resins, 12 , 13 polyamides, 14 − 17 and other polymers. 12 , 18 − 20 One particularly interesting application of itaconic acid is its ability to undergo the aza-Michael addition reaction with amines, followed by ring closure and the generation of a carboxylic acid functionalized pyrrolidone ring.…”

Reductive Amination/Cyclization of Methyl Levulinate with Aspartic Acid: Towards Renewable Polyesters with a Pendant Lactam Unit

“…The temperature was initially set at 180 °C to avoid the degradation of the monomer. A slight excess of diol was used because this is generally described to lead to higher‐molecular‐weight polymers . Table shows the yields, the number‐average molecular weight ( M n ), and the dispersity ( Đ ) measured by size‐exclusion chromatography (SEC) analysis of the crude polymer, for a survey of six catalysts (0.1 mol %).…”

“…Polyesters are used in many fields and have great potential as ecofriendly polymers because i) the ester functionality is a key point of degradability through hydrolysis and ii) they are very accessible from biobased building blocks . Miller and co‐workers have recently reported the synthesis of a hydroxy acid bearing a lactam group in the chain, leading to a poly(ester‐ co ‐amide) polymer after polycondensation (Scheme ) . The lactam group has also been incorporated from itaconic acid and diamines by Kaneko and co‐workers, or by the multicomponent 4CR‐Ugi reaction from LevOH by Hartweg and Becer …”

Biotic and Abiotic Synthesis of Renewable Aliphatic Polyesters from Short Building Blocks Obtained from Biotechnology

“…[8] The current production of itaconic acid is around 80 000 tons per year, [38] with ap otential increaseu pto 400 000 tons per year by 2020. [67,68] AA is one of the most important commodity chemicals, with ag lobal market of about 4m illion tons per year,w hich is mainly used for the production of Nylon 66 or polyesters. [59,63] Itaconic acid can be used as ab uilding block for the synthesis of curable polyesters or polyamides resins.…”

“…[64][65][66] Moreover,i taconic acid can be used as ap latform molecule to obtain aw ide range of chemical derivatives, such as g-butyrolactone, methacrylic acid, and pyrrolidones, throughh ydrogenation/reductionr eactions. [67,68] AA is one of the most important commodity chemicals, with ag lobal market of about 4m illion tons per year,w hich is mainly used for the production of Nylon 66 or polyesters. [11,57,47] At present, AA is mostly manufactured industrially through the oxidation of cyclohexanol or cyclohexanone.…”