TY - JOUR

T1 - Rapid tooling for rubber extrusion molding by digital light processing 3D printing with dual curable vitrimers

AU - Höller, Rita

AU - Hrbinič, Katja

AU - Reisinger, David

AU - Alabiso, Walter

AU - Schuschnigg, Stephan

AU - Fleisch, Mathias

AU - Waly, Christoph

AU - Rossegger, Elisabeth

AU - Schlögl, Sandra

N1 - Publisher Copyright: © 2024 Wiley-VCH GmbH.

PY - 2024/2/19

Y1 - 2024/2/19

N2 - For the manufacture of extrusion dies, three-dimensional (3D) printing with photopolymers offers numerous advantages including flexibility, high surface quality, decent build speed, low costs and a reduced amount of waste. However, the majority of photocurable resins used in vat photopolymerization 3D printing rely on acrylates, which entail 3D-printed objects with poor mechanical properties. In particular, the high brittleness limits their application in rapid tooling, for which tough materials with high glass transition temperatures (Tg) are required. In the present study, we highlight the use of dual curable acrylate-epoxy resins with dynamic covalent bonds for the direct fabrication of extrusion dies. During digital light processing (DLP) 3D printing the acrylate network is formed, whose toughness and thermal stability are significantly enhanced by the thermoactivated formation of a second network. By following a postbaking procedure, aminoglycidiyl monomers are cured with an anhydride hardener bearing bulky norbornene groups yielding interpenetrating polymer networks with a Tg > 100°C. The tertiary amine groups present in the structure of the aminoglycidyl derivatives do not only accelerate the ring-opening reaction but also act as internal catalysts and activate bond exchange reactions between free –OH groups and ester moieties available in the photopolymer. This is confirmed by rheometer studies showing a distinctive stress relaxation at elevated temperature and giving rise to a possible reprocessability of the 3D-printed dies. With a selected resin formulation, a set of dies is printed by DLP 3D printing, with which a highly filled rubber compound is successfully extruded. The results clearly show that dual curable resins with dynamic covalent bonds are a promising class of material for rapid tooling and pave the way towards a customized and convenient fabrication of extrusion dies for rubber processing.

AB - For the manufacture of extrusion dies, three-dimensional (3D) printing with photopolymers offers numerous advantages including flexibility, high surface quality, decent build speed, low costs and a reduced amount of waste. However, the majority of photocurable resins used in vat photopolymerization 3D printing rely on acrylates, which entail 3D-printed objects with poor mechanical properties. In particular, the high brittleness limits their application in rapid tooling, for which tough materials with high glass transition temperatures (Tg) are required. In the present study, we highlight the use of dual curable acrylate-epoxy resins with dynamic covalent bonds for the direct fabrication of extrusion dies. During digital light processing (DLP) 3D printing the acrylate network is formed, whose toughness and thermal stability are significantly enhanced by the thermoactivated formation of a second network. By following a postbaking procedure, aminoglycidiyl monomers are cured with an anhydride hardener bearing bulky norbornene groups yielding interpenetrating polymer networks with a Tg > 100°C. The tertiary amine groups present in the structure of the aminoglycidyl derivatives do not only accelerate the ring-opening reaction but also act as internal catalysts and activate bond exchange reactions between free –OH groups and ester moieties available in the photopolymer. This is confirmed by rheometer studies showing a distinctive stress relaxation at elevated temperature and giving rise to a possible reprocessability of the 3D-printed dies. With a selected resin formulation, a set of dies is printed by DLP 3D printing, with which a highly filled rubber compound is successfully extruded. The results clearly show that dual curable resins with dynamic covalent bonds are a promising class of material for rapid tooling and pave the way towards a customized and convenient fabrication of extrusion dies for rubber processing.

KW - dies

KW - dynamic photopolymers

KW - extrusion molding

KW - rapid tooling

KW - transesterification

UR - http://www.scopus.com/inward/record.url?scp=85188202498&partnerID=8YFLogxK

U2 - 10.1002/appl.202300133

DO - 10.1002/appl.202300133

M3 - Article

AN - SCOPUS:85188202498

VL - ??? Stand: 10. Juli 2024

JO - Applied research

JF - Applied research

SN - 2702-4288

IS - ??? Stand: 10. Juli 2024

M1 - e202300133

ER -