Polymer dispersity modulation by statistical copolymerization of (α-alkyl)acrylate monomers with disparate reactivity: Enhanced monomer conversion and tailored dispersity for dielectric elastomer application

• Published in: European polymer journal 2024-08, Vol.216, p.113265, Article 113265
• Main Authors: Hu, Keling, Zhang, Yaojing, Liu, Shun, Su, Chengkun, Sun, Jinming, Sun, Xin, Ma, Zhengfeng, Wu, Yang, Li, Bin
• Format: Article
• Language: English
• Subjects: Controlled polymerization; Dielectric elastomer; Itaconate; Polymer dispersity; Statistical copolymerization
• ISSN: 0014-3057; 1873-1945
• DOI: 10.1016/j.eurpolymj.2024.113265

A new approach for polymer dispersity (Ð) modulation is reported by the statistical copolymerization of sterically hindered itaconates with (meth)acrylate monomers with disparate reactivity. Ð values can be tuned in a broad range in a batch system. This strategy has demonstrated the sequential and topological versatility for Ɖ modulations, serving as a model system for Ð modulation in any segments of A-B diblock, B-A-B triblock, A-B-A triblock, and 3-arm star A-B diblock copolymers. [Display omitted] •A new strategy for polymer dispersity modulation is reported.•This method has demonstrated sequential and topological generality for Ð modulation in many types of block copolymers.•The segment after modulation can initiate polymerization of various types of monomers (e.g., methacrylate, acrylate).•The application scope of Ð modulation is expanded to thermoplastic dielectric elastomers as film capacitors . Polymer dispersity (Ð) is an important parameter in determining polymer properties. We report a new strategy for Ð modulation by statistically copolymerizing steric-hindered itaconates with methacrylate and acrylate monomers via organocatalyzed controlled radical polymerization. Due to the disparate monomer reactivity, Ð values can be tunable in a broad range (1.1–1.6) in a batch system. This strategy has demonstrated the sequential and topological generality for Ɖ modulations, serving as a model tool for Ð modulation in any segment of A-B diblock, B-A-B and A-B-A triblock, and 3-arm star A-B diblock copolymers. The unique aspects of this method are that the segment after Ð modulation can initiate polymerization of various types of monomers (e.g., methacrylate, acrylate) by the labile tertiary carbon-iodide chain-end without any external assistance or special initiator and monomer selection, the metal-free nature and the renewable substitution of petroleum-based methacrylate and acrylate monomers with bio-based itaconates without sacrificing inherent properties. This work broadens the application scope of Ð modulation to many other emerging technologies, such as antifreezing thermoplastic dielectric elastomers used as film capacitors in the field of energy storage.