How Is Rheology Involved in 3D Printing of Phase-Separated PVC-Acrylate Copolymers Obtained by Free Radical Polymerization

New auto-plasticised copolymers of poly(vinyl chloride)-r-(acrylate) and polyvinylchloride, obtained by radical polymerization, are investigated to analyse their capacity to be processed by 3D printing. The specific microstructure of the copolymers gives rise to a phase-separated morphology constituted by poly(vinyl chloride) (PVC) domains dispersed in a continuous phase of acrylate-vinyl chloride copolymer. The analysis of the rheological results allows the suitability of these copolymers to be assessed for use in a screw-driven 3D printer, but not by the fused filament fabrication method. This is due to the high melt elasticity of the copolymers, caused by interfacial tension between phases. A relationship between the relaxation modulus of the copolymers and the interlayer adhesion is established. Under adequate 3D-printing conditions, flexible and ductile samples with good dimensional stability and cohesion are obtained, as is proven by scanning electron microscopy (SEM) and tensile stress-strain tests.