In situ mechanical reinforcement of polyimine vitrimer via bioinspired crosslink mineralization

Abstract

Polyimines (PI) are vitrimer materials with unique Schiff base dynamic covalent chemistry. Various inorganic micro or nano fillers have been used to enhance the mechanical properties of PI materials. Inspired by natural biomineralization, a novel polyimine vitrimer composite is designed and prepared via a one‐pot synthesis. Briefly, diethylenetriamine and glutaraldehyde are used as the monomers of the PI matrix. Then a silica precursor, (3‐aminopropyl)trimethoxy silane is employed to develop silica nanoparticles within the formed PI matrix. The in situ generated silica nanoparticles with amine groups could act as the enhancing fillers and the crosslinkers in the artificial biomineralized silica reinforced polyimine composites. The optimized hybrid materials possessed enhanced mechanical properties, heat‐driven malleability, and limited recycling ability. Notably, the silica content (11.7%) is crucial to the mechanical performance of the PI matrix. This method may help to pave a new avenue on the simple fabrication of hybrid composites.

Construction of Mineralization Nanostructures in Polymers for Mechanical Enhancement and Functionalization

“…[18][19][20][21] In addition, atypical covalent bonding has also been reported, distinguished from non-covalent action, that requires a special design of functional groups to achieve. [22,23] This wisdom of natural selection in mollusk shells, sea urchin skeletons, lamellar bones and biogenic silica has already been demonstrated in fields such as biology, [24][25][26] medicine, [27][28][29] construction, [30][31][32][33] and composites. [34][35][36] In extensive research, the construction of mineralization is generally divided into two ways depending on the purposes: one is to utilize organic molecules to regulate inorganic nanostructures to generate the desired inorganic mineral or the organic-inorganic hybrid.…”

“…[39][40][41][42] While eyes are focused on the mineralization-modified polymer composites, endeavors to efficiently combine mineralization with matrix have resulted in the emergence of a diversity of novel multifunctional materials. For instance, hydrogels for cranial in situ regeneration, [43] high-strength polyimide vitrimers, [22] mineralized nanofiltration membranes with ultra-high separation efficiency, [44] and injectable mineralized hydrogels for tumor therapies. [45] Despite numerous advantages, constructing highly ordered mineralized nanostructures in highly viscous polymers remains a significant challenge.…”

“…[ 18–21 ] In addition, atypical covalent bonding has also been reported, distinguished from non‐covalent action, that requires a special design of functional groups to achieve. [ 22,23 ]…”

“…The SEM image (4) and the corresponding elemental mappings of 5) C and 6) Si of a carbonized ABSR-PI 16.7 composite sample treated by hydrofluoric acid. Reprinted with permission [22]. Copyright 2021, John Wiley and Sons.…”

Terpolymers of acrylonitrile, methyl acrylate, and 2‐acrylamido‐2‐methylpropane sulfonic acid for carbon fiber precursor: Effect of comonomers on the thermal stabilization of polyacrylonitrile copolymers

“…During this process, PAN filaments undergo cyclization, dehydrogenation, oxidation, and isomerization reactions. [11][12][13][14] And, the physical and chemical structure of the filaments undergoes many complex changes. Meanwhile, the PAN molecular chain gradually changes from a linear structure to a trapezoidal ring structure, a structure that allows the fibers to withstand higher temperature carbonization treatments.…”