β-Amino amide based covalent adaptable networks with high dimensional stability

Abstract

Catalyst-free reversible β-amino amides in covalent adaptable networks with reprocessability and high dimensional stability.

Fully Biobased Self-Healing and Recyclable Covalent Adaptable Networks Prepared via a Catalyst-Free Aza-Michael Reaction

“…The plausible disulfide bond exchange mechanism for the self-healing property of the CAN films is schematically shown in Figure f, where disulfide bonds of a segment (marked as red or blue) break and combine again with other segments (marked as blue-red) and/or the same segment. In this context, it should be mentioned that the reversible aza-Michael reaction also plays a significant role in the self-healing mechanism. , As our CANs have been constructed using disulfide linkages and aza-Michael bonds, we may consider that the self-healing nature of our CAN films is not only due to the disulfide bond exchange but also due to the contribution of the reversible aza-Michael reaction. However, the reversible aza-Michael reaction generally occurs at high temperatures. , As we have used a maximum temperature of 120 °C, we may expect a negligible contribution of the reversible aza-Michael reaction during the self-healing process of our prepared CAN films.…”

“…In this context, it should be mentioned that the reversible aza-Michael reaction also plays a significant role in the self-healing mechanism. 7,48 As our CANs have been constructed using disulfide linkages and aza-Michael bonds, we may consider that the self-healing nature of our CAN films is not only due to the disulfide bond exchange but also due to the contribution of the reversible aza-Michael reaction. However, the reversible aza-Michael reaction generally occurs at high temperatures.…”

Aza-Michael Chemistry for PDMS-Based Covalent Adaptable Elastomers: Design and Dual Role of the Silica Filler

“…On the other hand, because both amine- and acrylate-modified polydimethylsiloxanes (PDMSs) are readily available, we envisaged that a particularly attractive approach to prepare recyclable PDMS elastomers would be the use of the aza-Michael addition between acrylates and amines to form reversible β-amino esters (BAEs) during the curing process . This approach would build further on the in-house knowledge regarding the dynamicity of Michael adducts, − which our research group recently explored in the area of dynamic materials and has been further investigated by other groups in the meantime. − Although the facile utilization of aza-Michael addition chemistry in silicone network synthesis has been reported, the dynamic nature of the formed β-amino ester bonds in bulk silicone elastomers has been overlooked to the best of our knowledge.…”

Oxidative Polymer Degradation via Cope Elimination

“…To address challenges in plastic persistence, it is vital to develop highly tunable, degradable materials. − With this in mind, poly(β-amino esters) (PBAEs) and poly(amido amines) (PAMAMs) have garnered interest in biomedical and materials science due to their facile synthesis, controllable degradation lifetime, and biocompatibility. − These materials are typically prepared via bulk aza-Michael polymerization of diacrylates/acrylamides with primary amines. , This combinatorial approach allows for the preparation of materials libraries with highly customizable backbone and pendent group chemistries without the need for purification. − Because of this structural diversity and ease of synthesis, PBAEs and PAMAMs have been extensively investigated as degradable polymeric platforms in gene delivery, ,, bioimaging, , three-dimensional (3D) printing, , and dynamic covalent networks. − …”