Progress in the Free and Controlled Radical Homo‐ and Co‐Polymerization of Itaconic Acid Derivatives: Toward Functional Polymers with Controlled Molar Mass Distribution and Architecture

• Published in: Macromolecular rapid communications. Vol. 42; no. 4; pp. e2000546 - n/a
• Main Authors: Sollka, Lea, Lienkamp, Karen
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 01.02.2021
• Subjects: Accessibility; Acids; Addition polymerization; atom‐transfer radical polymerization (ATRP); Chain transfer; Derivatives; diitaconate; Free radical polymerization; free radical polymerization (FRP); Free radicals; Itaconic acid; itaconimide; Mass distribution; Monomers; poly(diitaconates); Polydispersity; Polymerization; Polymers; Renewable resources; reversible addition fragmentation chain transfer polymerization (RAFT); Sustainable yield; itaconic acid; itaconimide; free radical polymerization (FRP); poly(diitaconates); reversible addition fragmentation chain transfer polymerization (RAFT); atom-transfer radical polymerization (ATRP); diitaconate
• ISSN: 1022-1336; 1521-3927; 1521-3927
• DOI: 10.1002/marc.202000546

Polymeric derivatives of itaconic acid are becoming increasingly more interesting for research and industry because itaconic acid is accessible from renewable resources. In spite of the structural similarity of poly(itaconic acid derivatives) to poly(methacrylates), they are much less reactive, homopolymerize only sluggishly by free radical polymerization (FRP), and are often obtained with low molar masses and conversions. This has so far limited their use. The reasons for the low reactivity of itaconic acid derivatives (including itaconimides, diitaconates, and diitaconamides) are combined steric and electronic effects, as demonstrated by the body of literature on the FRP homopolymerization kinetics of these monomers which is summarized herein. These problems can be solved to a large extent by using controlled radical polymerization (CRP) techniques, notably atom transfer radical polymerization (ATRP) and reversible addition and fragmentation chain transfer radical polymerization (RAFT). By optimizing the reaction conditions for the ATRP and RAFT of itaconic acid derivatives, in particular the reaction temperature, linear relations between molar mass and conversion are obtained in many cases, and homopolymers with high molar masses and reasonably narrow polydispersity indices become accessible. This review presents the state‐of‐the‐art FRP and CRP of itaconic acid derivatives, and highlights functional polymers obtained by these methods. Homo‐ and co‐polymers with high functional group density can be obtained by free and controlled radical polymerization of itaconic acid derivatives, including itaconimides, diitaconates, and diitaconamides.