Maleimide‐styrene‐butadiene terpolymers: acrylonitrile‐butadiene‐styrene inspired photopolymers for additive manufacturing

Abstract

The terpolymer acrylonitrile‐butadiene‐styrene (ABS) is a widely used thermoplastic material due to its excellent mechanical properties, especially high toughness. However, the monomer system of ABS cannot be feasibly photopolymerized due to its reactivity, opacity and monomer volatility. We show the transfer of an ABS microstructure to photopolymers via monomer systems designed to mimic ABS while remaining photopolymerizable. Acrylonitrile was substituted by more reactive and less volatile maleimides, of which the N substituent influences crosslinking considerably. Instead of styrene, less volatile derivatives were utilized as comonomers. Poly(butadiene) was introduced as cheap, readily available and non‐volatile rubber. The resulting maleimide‐styrene‐poly(butadiene) networks exhibit varying microphase separations and simultaneous transparency. While optimized materials cannot quite exhibit the yield strain of hot‐pressed ABS filament, their toughness partly exceeds that of ABS. Superior thermal stabilities and glass transition temperatures up to 190 °C were observed. Finally, stereolithographic printing of one tuned monomer system was conducted. © 2021 The Authors. Polymer International published by John Wiley & Sons Ltd on behalf of Society of Industrial Chemistry.

From Unregulated Networks to Designed Microstructures: Introducing Heterogeneity at Different Length Scales in Photopolymers for Additive Manufacturing

“…A first example in this regard has been published more recently, where butadiene rubber was added to a photopolymerizable maleimide/styrene formulation to mimic traditional ABS materials, which can be printed. 155 In this case, the rubbery phase was linked with the photopolymer network covalently via its main chain double bonds. Another type of incorporation could be block copolymers, which are only incorporated into the network via their chain ends, which would facilitate chain slipping and reversible physical interactions before fracture (T1, T3).…”

“…Successful AFM imaging is very sensitive to the sample’s surface quality, and a specific initial setting cannot consistently be applied to different samples . As a result, distinguishing rigidity and identifying the hard and soft domains is ideally achieved by tapping mode phase imaging combined with force distance spectroscopy. , Alternatively, fully quantitative imaging modes are efficient. , …”

“…Processing such materials with AMTs would certainly enhance their attractiveness for biomedical applications. A first example in this regard has been published more recently, where butadiene rubber was added to a photopolymerizable maleimide/styrene formulation to mimic traditional ABS materials, which can be printed . In this case, the rubbery phase was linked with the photopolymer network covalently via its main chain double bonds.…”

“…Schematic drawing of the plastic zone in front of the crack tip and an example of a plastic zone in PVC-C (chlorinated poly­(vinyl chloride)). Reprinted from ref with permission from Hanser.…”

Heat-Resistant Phthalonitrile-Based Resins for 3D Printing via Vat Photopolymerization

“…Recently, our research group has successfully designed a low-melting and self-curing phthalonitrile monomer grafted with a maleimide group 4-[3-(2,5-dione-1 H -pyrrole-1-yl)­phenoxy]­benzene-1,2-dicarbonitrile (PNB-M) . We consider the PNB-M monomer to be suitable for VP for a few reasons: the maleimide group is photopolimerizable and might undergo radical copolymerization with acrylates during VP processing and thermal postcuring; − low melting temperature of the monomer might lead to high solubility in photopolymer composition; and due to its autocatalytic nature, phthalonitrile polymerization might be initiated without addition of amines.…”