Mono vs. Difunctional Coumarin as Photoinitiators in Photocomposite Synthesis and 3D Printing

Mahmoud Rahal,Tayssir Hamieh,Jacques Lalevée,Frédéric Dumur,Bernadette Graff,Joumana Toufaily,Haifaa Mokbel

doi:10.3390/catal10101202

Abstract

This work is devoted to investigate three coumarin derivatives (Coum1, Coum2, and Coum3), proposed as new photoinitiators of polymerization when combined with an additive, i.e., an iodonium salt, and used for the free radical polymerization (FRP) of acrylate monomers under mild irradiation conditions. The different coumarin derivatives can also be employed in three component photoinitiating systems with a Iod/amine (ethyl 4-dimethylaminobenzoate (EDB) or N-phenylglycine (NPG)) couple for FRP upon irradiation with an LED @ 405 nm. These compounds showed excellent photoinitiating abilities, and high polymerization rates and final conversions (FC) were obtained. The originality of this work relies on the comparison of the photoinitiating abilities of monofunctional (Coum1 and Coum2) vs. difunctional (Coum3) compounds. Coum3 is a combined structure of Coum1 and Coum2, leading to a sterically hindered chemical structure with a relatively high molecular weight. As a general rule, a high molecular weight should reduce the migration of initiating molecules and favor photochemical properties such as photobleaching of the final polymer. As attempted, from the efficiency point of view, Coum3 can initiate the FRP, but a low reactivity was observed compared to the monofunctional compound (Coum1 and Coum2). Indeed, to study the photochemical and photophysical properties of these compounds, different parameters were taken into account, e.g., the light absorption and emission properties, steady state photolysis, and fluorescence quenching. To examine these different points, several techniques were used including UV-visible spectroscopy, real-time Fourier Transform Infrared Spectroscopy (RT-FTIR), fluorescence spectroscopy, and cyclic voltammetry. The photochemical mechanism involved in the polymerization process is also detailed. The best coumarins investigated in this work were used for laser writing (3D printing) experiments and also for photocomposite synthesis containing glass fibers.

Highlights

During the last decade, photochemical reactions showed a huge number of industrial and academic applications such as UV-curing, solar cells, and photopolymerization [1,2]
Two- or three-component systems such as Coum/Iod (0.1%/1% w/w) or Coum/Iod/amine (0.1%/1%/1% w/w/w) were quite efficient and could efficiently initiate the polymerization process. This is related to the photooxidation process between Iod and coumarin and to the formation of a charge transfer complex (CTC) between Iod and NPG [Iod-NPG] CTC
The different absorption spectra are characterized by two main absorption bands, one located in the near-UV range (

Summary

Introduction

Photochemical reactions showed a huge number of industrial and academic applications such as UV-curing, solar cells, and photopolymerization [1,2]. These reactions can advantageously replace thermally-based chemical processes due to their many advantages [3,4] such. Coumarins are used in flavoring food and in cosmetic products such as fragrances [10,11] These compounds are characterized by high photoluminescence quantum yields and can be used as fluorescent chromophores for various applications [12]. Heterocyclic fluorescent compounds have been used in several research fields such as molecular probes for biochemical research [13], emitters for electroluminescent devices [14], fluorescent probes for heavy metal sensing [15], molecules exhibiting biological activities [16] or active layers for photovoltaic applications [17]

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Discussion

Conclusion