3995024

Unreacted amine groups: Indispensable keys to unlock imine bonds in dynamic networks

Date
March 20, 2024
Explore related products in the following collection:

Several strategic areas rely on the development of polymers, but the growth of plastic waste urges for new materials combining desired mechanical properties and recyclability. A promising solution is the partial/total replacement of permanent crosslinks by dynamic bonds, which allows for designing easily recyclable polymers without loss of their mechanical properties in a desired temperature range.
Among the possible dynamic bonds, imine functionalities are promising candidates as they undergo rapid exchange and can be formed in the absence of catalysts with water as the only byproduct of the reaction (Fig.1). Imines are formed via condensation of primary amines with carbonyl compounds and can undergo hydrolysis, transamination, and metathesis reactions depending on the concentration of water and unreacted amines. While these mechanisms are well-established in chemistry and biology literature, the utilization of imine bonds as a dynamic moiety in long-chain polymers is recent. Hence, the crucial role of unreacted amines, even in residual amounts, as a mediator of metathesis exchange, is often overlooked in the design and description of these networks. Therefore, we seek to provide a mechanistic description of the dynamic and viscoelastic behavior of telechelic and pendant functionalized model systems based on polydimethylsiloxane (PDMS) bearing imine bonds. We combine linear rheology and broadband dielectric spectroscopy to systematically show that in the absence of unreacted amines, network rearrangement based on imine exchange does not occur at temperatures reasonably lower than polymer degradation. Also, we show that the energy barrier of bond rearrangement is dictated by the theoretical availability of amine groups in the system and not by their cross-link density.
Reversible processes involving imine bonds: imine formation and hydrolysis (top),  transimination (middle), and metathesis (bottom).

Reversible processes involving imine bonds: imine formation and hydrolysis (top), transimination (middle), and metathesis (bottom).


Related Products

Thumbnail for Design of multi-functional intrinsic self-healing polymers with tailored hydrogen bonding
Design of multi-functional intrinsic self-healing polymers with tailored hydrogen bonding
The structural design of self-healing materials determines the ultimate performance and logevity of the product in a wide range of applications…
Thumbnail for Synthesis of hydrolytically degradable block copolymer nanoparticles via polymerization-induced self-assembly in aqueous media
Synthesis of hydrolytically degradable block copolymer nanoparticles via polymerization-induced self-assembly in aqueous media
Polymerization-Induced Self-Assembly (PISA) is a platform technology that can be used for the synthesis of block copolymer nanoparticles as a concentrated colloidal dispersion…
Thumbnail for Data-driven development of polymer microparticles
Data-driven development of polymer microparticles
Long-acting injectables (LAIs) can offer several advantages over conventional medicines, including prolonged therapeutic effect and improvements in patient adherence. Several types of LAIs have been approved for human use, including drug-loaded polymer microparticles (MPs)…