Next Article in Journal
Rhodium Nanoparticles Stabilized by PEG-Tagged Imidazolium Salts as Recyclable Catalysts for the Hydrosilylation of Internal Alkynes and the Reduction of Nitroarenes
Previous Article in Journal
Steric Effects of Mesoporous Silica Supported Bimetallic Au-Pt Catalysts on the Selective Aerobic Oxidation of Aromatic Alcohols
Previous Article in Special Issue
Visible Light Electromagnetic Interaction of PM567 Chiral Dye for Asymmetric Photocatalysis, a First-Principles Investigation
Open AccessFeature PaperArticle

Novel Push–Pull Dyes Derived from 1H-cyclopenta[b]naphthalene-1,3(2H)-dione as Versatile Photoinitiators for Photopolymerization and Their Related Applications: 3D Printing and Fabrication of Photocomposites

1
Université de Haute-Alsace, CNRS, IS2M UMR 7361, F-68100 Mulhouse, France
2
Université de Strasbourg, F-67081 Strasbourg, France
3
Aix Marseille Univ, CNRS, ICR UMR 7273, F-13397 Marseille, France
4
Research School of Chemistry, Australian National University, Canberra ACT 2601, Australia
*
Authors to whom correspondence should be addressed.
Catalysts 2020, 10(10), 1196; https://doi.org/10.3390/catal10101196
Received: 19 September 2020 / Revised: 4 October 2020 / Accepted: 5 October 2020 / Published: 15 October 2020
(This article belongs to the Special Issue Progression in Photocatalytic Materials for Efficient Performance)
A series of eleven push–pull chromophores with specific structures have been designed for the free radical polymerization of acrylates, but also for the fabrication of photocomposites and 3D-printed structures. New photoinitiating systems comprising the different push–pull dyes showed excellent photochemical reactivities at 405 nm. Notably, polymerization reactions could be initiated with light-emitting diodes (LEDs) which constitute a unique opportunity to promote the free radical polymerization under mild conditions, i.e., low light intensity (e.g., sunlight) and under air. Photopolymerization is an active research field, and push–pull dyes have already been investigated for this purpose. Besides, it remains of crucial interest to investigate new reactive structures capable of efficiently initiating photopolymerization reactions. The plausible potential of these structures to act as efficient photoinitiators in vat photopolymerization (or 3D printing) and fabrication of photocomposites prompts us to select eleven new push–pull dyes to design multi-component photoinitiating systems activable with LEDs emitting at 405 nm. Precisely, a tertiary amine, i.e., ethyl dimethylaminobenzoate (EDB) used as an electron/hydrogen donor and an iodonium salt used as an electron acceptor were selected to behave as powerful co-initiators to construct three-component photoinitiating systems (PISs) with the different push–pull dyes. Among these new PISs, dye 8 and 9-based PISs could efficiently promote the free radical photopolymerization of acrylates upon exposure to a LED emitting at 405 nm also upon sunlight irradiation, highlighting their huge performance. Photoinitiating abilities could be explained on the basis of steady state photolysis experiments. Fluorescence measurements and electron spin resonance (ESR) spin-trapping experiments were also performed to obtain a deeper insight into the chemical mechanisms supporting the polymerization reaction and determine the way the initiating species, i.e., the radicals, are observed. Finally, two investigated dye-based PISs were applied to the fabrications of photocomposites. Three-dimensional patterns with excellent spatial resolutions were generated by the laser writing technique to identify the effects of photopolymerization of acrylates both in the absence and presence of fillers (silica). Interestingly, comparison between the 3D objects fabricated by the PISs/monomer systems and the PISs/monomer/filler photocomposites indicates that the newly designed photocomposites are suitable for practical applications. View Full-Text
Keywords: push–pull dye; free radical polymerization; three-component system; LED; 3D printing; naphthalene-1,3-dione push–pull dye; free radical polymerization; three-component system; LED; 3D printing; naphthalene-1,3-dione
Show Figures

Graphical abstract

MDPI and ACS Style

Sun, K.; Liu, S.; Pigot, C.; Brunel, D.; Graff, B.; Nechab, M.; Gigmes, D.; Morlet-Savary, F.; Zhang, Y.; Xiao, P.; Dumur, F.; Lalevée, J. Novel Push–Pull Dyes Derived from 1H-cyclopenta[b]naphthalene-1,3(2H)-dione as Versatile Photoinitiators for Photopolymerization and Their Related Applications: 3D Printing and Fabrication of Photocomposites. Catalysts 2020, 10, 1196.

Show more citation formats Show less citations formats
Note that from the first issue of 2016, MDPI journals use article numbers instead of page numbers. See further details here.

Article Access Map by Country/Region

1
Search more from Scilit
 
Search
Back to TopTop