Working Paper Article Version 1 This version is not peer-reviewed

Kinetics Analysis of Copper Complex Photoredox Catalyst: Roles of Oxygen, Thickness, and Optimal Concentration for Radical/Cationic Hybrid Photopolymerization

Version 1 : Received: 25 May 2021 / Approved: 25 May 2021 / Online: 25 May 2021 (09:50:35 CEST)

How to cite: Lin, J.; Lalevee, J.; Cheng, D. Kinetics Analysis of Copper Complex Photoredox Catalyst: Roles of Oxygen, Thickness, and Optimal Concentration for Radical/Cationic Hybrid Photopolymerization. Preprints 2021, 2021050597 Lin, J.; Lalevee, J.; Cheng, D. Kinetics Analysis of Copper Complex Photoredox Catalyst: Roles of Oxygen, Thickness, and Optimal Concentration for Radical/Cationic Hybrid Photopolymerization. Preprints 2021, 2021050597

Abstract

This article presents, for the first time, the kinetics and the general conversion features of a 3-initiator system (A/B/N), based on proposed mechanism of Mokbel et al, for both free radical polymerization (FRP) of acrylates and the free radical promoted cationic polymerization (CP) of epoxides using copper complex as the initiator. Higher FRP and CP conversion can be achieved by co-initiators concentration [B] and [N], via the dual function of (i) regeneration [A], and (ii) generation of extra radicals S' and S. The FRP and CP conversion is proportional to, respectively, the nonlinear and linear power of bI[A][B], where b and I are the absorption coefficient and the light intensity, respectively. System in air has lower conversion than in laminate due to the oxygen inhibition effects. For thick samples (with thickness z), there is an optimal concentration [A*] which is inverse proportional (bzI), in contrast with very thin sample, in which the conversion is an increasing function of [A] and [B]. The unique feature of dark polymerization in CP conversion enables the polymerization to continue in living mode, in contrasts with that of the radical-mediated pathway in most conventional FRP. The measured results of Mokbel et al are well analyzed and matching the predicted features of our modeling.

Subject Areas

polymerization kinetics; photoinitiator; free radical, cationic polymerization, copper complex, photoredox catalyst.

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