Additive manufacturing or 3D printing of materials is a prominent process technology which involves the fabrication of materials layer-by-layer or point-by-point in a subsequent manner. With recent advancements in additive manufacturing, the technology has excited a great potential for extension of simple designs to complex multi-material geometries. Vat photopolymerization is a subdivision of additive manufacturing which possesses many attractive features, including excellent printing resolution, high dimensional accuracy, low-cost manufacturing, and the ability to spatially control the material properties. However, the technology is currently limited by design strategies, material chemistries, and equipment limitations. This review aims to provide readers with a comprehensive comparison of different additive manufacturing technologies along with detailed knowledge on advances in multi-material vat photopolymerization technologies. Furthermore, we describe popular material chemistries both from the past and more recently, along with future prospects to address the material-related limitations of vat photopolymerization. Examples of the impressive multi-material capabilities inspired by nature which are applicable today in multiple areas of life are briefly presented in the applications section. Finally, we describe our point of view on the future prospects of 3D printed multi-material structures as well as on the way forward towards promising further advancements in vat photopolymerization.

The polymer class of poly(2-oxazoline)s currently is under intensive investigation due to the versatile properties that can be tailor-made by the variation and manipulation of the functional groups they bear. In particular their utilization in the biomedic(in)al field is the subject of numerous studies. Given the mechanism of the cationic ring-opening polymerization, a plethora of synthetic strategies exists for the preparation of poly(2-oxazoline)s with dedicated functionality patterns, comprising among others the functionalization by telechelic end-groups, the incorporation of substituted monomers into (co)poly(2-oxazoline)s, and polymeranalogous reactions. This review summarizes the current state-of-the-art of poly(2-oxazoline) preparation and showcases prominent examples of poly(2-oxazoline)-based materials, which are retraced to the desktop-planned synthetic strategy and the variability of their properties for dedicated applications.

Natural and synthetic coumarin derivatives have gained increased attention in the design of functional polymers and polymer networks due to their unique optical, biological, and photochemical properties. This review provides a comprehensive overview over recent developments in macromolecular architecture and mainly covers examples from the literature published from 2004 to 2020. Along with a discussion on coumarin and its photochemical properties, we focus on polymers containing coumarin as a nonreactive moiety as well as polymer systems exploiting the dimerization and/or reversible nature of the [2πs + 2πs] cycloaddition reaction. Coumarin moieties undergo a reversible [2πs + 2πs] cycloaddition reaction upon irradiation with specific wavelengths in the UV region, which is applied to impart intrinsic healability, shape-memory, and reversible properties into polymers. In addition, coumarin chromophores are able to dimerize under the exposure to direct sunlight, which is a promising route for the synthesis and cross-linking of polymer systems under “green” and environment-friendly conditions. Along with the chemistry and design of coumarin functional polymers, we highlight various future application fields of coumarin containing polymers involving tissue engineering, drug delivery systems, soft robotics, or 4D printing applications.

Polymers with light-responsive groups have gained increased attention in the design of functional materials, as they allow changes in polymers properties, on demand, and simply by light exposure. For the synthesis of polymers and polymer networks with photolabile properties, the introduction o-nitrobenzyl alcohol (o-NB) derivatives as light-responsive chromophores has become a convenient and powerful route. Although o-NB groups were successfully exploited in numerous applications, this review pays particular attention to the studies in which they were included as photo-responsive moieties in thin polymer films and functional polymer coatings. The review is divided into four different sections according to the chemical structure of the polymer networks: (i) acrylate and methacrylate; (ii) thiol-click; (iii) epoxy; and (iv) polydimethylsiloxane. We conclude with an outlook of the present challenges and future perspectives of the versatile and unique features of o-NB chemistry.

As an energy-efficient additive manufacturing process, vat photopolymerization 3D-printing has become a convenient technology to fabricate functional devices with high resolution and freedom in design. However, due to their permanently crosslinked network structure, photopolymers are not easily reprocessed or repaired. To improve the environmental footprint of 3D-printed objects, herein, we combine the dynamic nature of hydroxyl ester links, undergoing a catalyzed transesterification at elevated temperature, with an acrylate monomer derived from renewable resources. As a sustainable building block, we synthesized an acrylated linseed oil and mixed it with selected thiol crosslinkers. By careful selection of the transesterification catalyst, we obtained dynamic thiol-acrylate resins with a high cure rate and decent storage stability, which enabled the digital light processing (DLP) 3D-printing of objects with a structure size of 550 µm. Owing to their dynamic covalent bonds, the thiol-acrylate networks were able to relax 63% of their initial stress within 22 min at 180 °C and showed enhanced toughness after thermal annealing. We exploited the thermo-activated reflow of the dynamic networks to heal and re-shape the 3D-printed objects. The dynamic thiol-acrylate photopolymers also demonstrated promising healing, shape memory, and re-shaping properties, thus offering great potential for various industrial fields such as soft robotics and electronics.

Poly(2-oxazoline) networks with varying swelling degrees and varying hydrophilicity can be synthesized from 2-ethyl-2-oxazoline, 2-nonyl-2-oxazoline, 2-9’-decenyl-2-oxazoline and 2,2’-tetramethylene-bis-2-oxazoline in one-pot/one-step strategies. These gels can be loaded with organic molecules, such as fluorescein isothiocyanate, either during the polymerization (covalent attachment of the dye) or according to post-synthetic swelling/deswelling strategies (physical inclusion of the dye). Surface functionalization of ground gels by thiol-ene reactions with cysteine-bearing peptides exhibiting the arginine-glycine-aspartic acid (RGD) motif yields microparticles with enhanced recognition of human cancer cells compared to healthy endothelial cells.