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Free Radical Photopolymerization and 3D Printing Using Newly Developed Dyes: Indane-1,3-Dione and 1H-Cyclopentanaphthalene-1,3-Dione Derivatives as Photoinitiators in Three-Component Systems

Date

2020

Authors

Sun, Ke
Pigot, Corentin
Chen, Hong
Nechab, Malek
Gigmes, Didier
Morlet-Savary, Fabrice
Graff, Bernadette
Liu, Shaohui
Xiao, Pu
Dumur, Frederic

Journal Title

Journal ISSN

Volume Title

Publisher

MDPI

Abstract

The design of photoinitiating systems with excellent photochemical reactivities at 405nm LED is one of the obstacles to efficiently promote free radical polymerization in mild conditions (e.g., low light intensity, under air). Here, our actual search for new multicomponent photoinitiating systems at 405nm LED prompts us to develop new dyes based on push-pull structures. In the present paper, we chose two series of new dyes which possess indane-1,3-dione and 1H-cyclopenta naphthalene-1,3-dione groups as the electron-withdrawing groups, since they have the great potential to behave as sensitive and remarkable photoinitiators in vat photopolymerization/3D printing. When incorporated with a tertiary amine (ethyl dimethylaminobenzoate EDB, used as electron/hydrogen donor) and an iodonium salt (used as electron acceptor) as the three-component photoinitiating systems (PISs), and among a series of 21 dyes, 10 of them could efficiently promote the free radical photopolymerization of acrylates. Interestingly, steady state photolysis experiments revealed different behaviors of the dyes. Fluorescence experiments and free energy change calculations for redox processes were also carried out to investigate the relevant chemical mechanisms. Additionally, the formation of radicals from the investigated PISs was clearly observed by electron spin resonance (ESR) spin-trapping experiments. Finally, stereoscopic 3D patterns were successfully fabricated by the laser writing technique. In this work, the use of push-pull dyes based on the naphthalene scaffold as photoinitiators of polymerization is reported for the first time in a systematic study aiming at investigating the structure-performance relationship for irradiation carried out at 405 nm. By carefully selecting the electron donors used in the two series of push-pull dyes, novel and high-performance photoinitiating systems operating at 405 nm are thus proposed.

Description

Keywords

push–pull dye, free radical polymerization, three-component system, LED, 3D printing

Citation

Source

Catalysts

Type

Journal article

Book Title

Entity type

Access Statement

Open Access

License Rights

Creative Commons Attribution (CC BY) license

DOI

10.3390/catal10040463

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