Multifunctional Block Copolymers, Acting as Recycling Aids, by Atom Transfer Radical Polymerization

Block copolymers utilizing oligomeric poly(pentylene‐co‐hexylene carbonate)diol modified with 2,4‐diisocyanatotoluene and further with 2‐bromo‐N‐(3‐hydroxypropyl)‐2‐methylpropanamide were synthesized and utilized as Activators ReGenerated by Electron Transfer Atom Transfer Radical Polymerization macroinitiators to obtain a first generation of multifunctional recycling additives with poly(glycidyl methacrylate‐co‐butyl methacrylate‐co‐methyl methacrylate) side chains, which could act as chain extenders. Then, chosen additive was reacted with a radical scavenger, 3,5‐ditertbutyl‐4‐hydroxybenzoic acid (DHBA), to obtain a second generation of reactive additives. Those copolymers had different numbers of epoxy groups per polymer chain, and different number of epoxides opened with DHBA, hence showed a range of properties, and were utilized as reactive modifiers for polylactide (PLA) extrusion melting. The first‐generation modifiers caused an increase in PLA's blends relative melt viscosity, stabilized material properties, and enhanced impact strength, while the second‐generation modifiers with more than 8 % of epoxide ring opened showed worse properties. However, they managed to suppress the UV degradation of PLA blend plates. Multifunctional, reactive additives for PLA recycling, which could act both as antioxidants and chain extenders, were synthesized utilizing ARGET ATRP. They proved to stabilize and, in some cases, even improve PLA's viscosity and mechanical properties during long (30 minutes) extrusion, which imitated 5 recycling acts.