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

Abstract

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.

Monomers and Macromolecular Materials from Renewable Resources: State of the Art and Perspectives

“…The polymerization of itaconic acid, in turn, was considered of limited interest up to a few years ago using conventional polyaddition initiators, but the scenario was recently changed by the possibility of using controlled radical polymerization techniques, notably atom transfer radical polymerization (ATRP) and reversible addition and fragmentation chain transfer radical polymerization (RAFT). The topic was discussed in a very interesting and complete monograph that tackled the opportunities of preparing itaconic acid-based polymers with controlled molar mass distributions and architectures [ 162 ].…”

Recent Advances in Biotechnological Itaconic Acid Production, and Application for a Sustainable Approach

“…This biopolymer is suitable for manufacturing various materials like intelligent food packaging, medication delivery, elastomers, hydrogels in water treatment, antimicrobial biofilms, and several other products [ 105 ]. An important aspect that has to be dissected through the production of these new bio-based polymers is their impact on sustainable development [ 106 ]. Consequently, besides the life-cycle assessment of these bio-polymers, essential aspects that have to be considered are the product properties intended to fulfill particular market requirements.…”

Playing construction with the monomer toy box for the synthesis of multi‐stimuli responsive copolymers by reversible deactivation radical polymerization protocols

“…Itaconic acid derivatives are obtained from carbohydrates fermentation by fungi. Even though they react sluggishly in FRP conditions, ATRP and RAFT have been successful at obtaining copolymers containing itaconic acid derivatives 24 . For example, pH‐ and temperature‐sensitive random copolymers of NIPAAm and itaconamic acid were obtained by RAFT in Rwei's group 240,241 .…”

“…However, RDRPs are of wide scope and relatively user‐friendly, and have therefore become a fundamental tool in the field of stimuli‐responsive materials. One of the aims of research focused on RDRPs is to assess the scope of different protocols for the reliable polymerization of different kinds of vinyl monomers 20–26 . At the next level of complexity, conditions are sought to ensure a good balance of reactivity of different monomers in order to obtain truly random copolymers 27–33 .…”