A Circular and Tacticity‐Independent Crystalline Mono‐Substituted Nylon‐6 Platform: Unexpected Large Positional Effects on Crystallizability and Performance

ABSTRACT Seeking recyclable, more sustainable alternatives to nylon 6 has drawn much attention, but achieving its variants with both crystallinity and enhanced recyclability still remains a challenge. Here, by utilizing bio‐derivable mono‐substituted racemic lactam monomers, we reveal surprisingly large effects of methyl substitution positions on the nylon‐6 backbone on crystallizability, thermomechanical performance, and recyclability of the resulting atactic nylon‐6 variants. While γ‐methyl substitution gives an amorphous nylon, all other four methyl‐substitution positions (α, β, δ, and ε) afford, unexpectedly, crystalline nylons with melting temperatures ranging from 145°C to 200°C and tunable mechanical performance from being stiff and strong (α, ε) to ductile (β, δ). Investigations reveal that the crystallinity of atactic nylons arises independently of stereoregularity, which is driven by the amide backbone with robust hydrogen‐bonding interactions and countered by the chain flexibility regulated by the substitution position. These nylons can be chemically recycled back to their parent monomers with high isolated yields up to 92%, enabling a circular, tacticity‐independent crystalline nylon platform.