Journal
MACROMOLECULAR RAPID COMMUNICATIONS
Volume 42, Issue 4, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/marc.202000546
Keywords
atom‐ transfer radical polymerization (ATRP); diitaconate; free radical polymerization (FRP); itaconic acid; itaconimide; poly(diitaconates); reversible addition fragmentation chain transfer polymerization (RAFT)
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Funding
- Projekt DEAL
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Polymeric derivatives of itaconic acid are of increasing interest due to their renewable sources. However, these derivatives have low reactivity and limited use compared to poly(methacrylates). Controlled radical polymerization techniques, such as ATRP and RAFT, have been shown to improve the reactivity and quality of these polymers.
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.
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