Biosourced and biodegradable
polyesters like poly(butylene succinate-co-butylene
adipate) (PBSA) are gaining traction as promising
alternatives to oil-based thermoplastics for single-use applications.
However, the mechanical and rheological properties of PBSA are affected
by its thermomechanical sensitivity during its melt processing, also
hindering PBSA mechanical recycling. Traditional reactive melt processing
(RP) methods use chemical additives to counteract these drawbacks,
compromising sustainability. This study proposes a green reactive
method during melt compounding for PBSA based on a comprehensive understanding
of its thermomechanical degradative behavior. Under the hypothesis
that controlled degradative paths during melt processing can promote
branching/recombination reactions without the addition of chemical
additives, we aim to enhance PBSA rheological and mechanical performance.
An in-depth investigation of the in-line rheological behavior of PBSA
was conducted using an internal batch mixer, exploring parameters
such as temperature, screw rotation speed, and residence time. Their
influence on PBSA chain scissions, branching/recombination, and cross-linking
reactions were evaluated to identify optimal conditions for effective
RP. Results demonstrate that specific processing conditions, for example,
twelve minutes processing time, 200 °C temperature, and 60 rpm
screw rotation speed, promote the formation of the long chain branched
structure in PBSA. These structural changes resulted in a notable
enhancement of the reacted PBSA rheological and mechanical properties,
exhibiting a 23% increase in elastic modulus, a 50% increase in yield
strength, and an 80% increase in tensile strength. The RP strategy
also improved PBSA mechanical recycling, thus making it a potential
replacement for low-density polyethylene (LDPE). Ultimately, this
study showcases how finely controlling the thermomechanical degradation
during reactive melt processing can improve the material’s
properties, enabling reliable mechanical recycling, which can serve
as a green approach for other biodegradable polymers.