Preprint Article Version 2 Preserved in Portico This version is not peer-reviewed

Modeling the Dual-Function Effects of Free Radical and Cationic Hybrid-Photopolymerization in Iodonium/Amine System

Version 1 : Received: 10 July 2021 / Approved: 14 July 2021 / Online: 14 July 2021 (12:03:25 CEST)
Version 2 : Received: 1 June 2022 / Approved: 2 June 2022 / Online: 2 June 2022 (04:19:03 CEST)

How to cite: Lin, J.; Chen, K. Modeling the Dual-Function Effects of Free Radical and Cationic Hybrid-Photopolymerization in Iodonium/Amine System. Preprints 2021, 2021070327. https://doi.org/10.20944/preprints202107.0327.v2 Lin, J.; Chen, K. Modeling the Dual-Function Effects of Free Radical and Cationic Hybrid-Photopolymerization in Iodonium/Amine System. Preprints 2021, 2021070327. https://doi.org/10.20944/preprints202107.0327.v2

Abstract

The synergistic features of a three-component, photoinitiating system (A/B/C) based on the measured data and proposed mechanism of Liu et al. are analyzed. The co-initiators/additives B and C have dual-functions of : (i) regeneration of photoinitiator A, and (ii) generation of extra radicals for enhanced conversion efficacy (CE). The synergistic effects led to higher CE for both free radical polymerization (FRP) and cationic polymerization (CP). The CE of FRP has 3 terms due to the direct (tyep-I) coupling of the triplet state of A with the monomer (M) and the coupling of the two radicals, R and R', with M. The CE of CP has a transient state proportional to the effective absorption constant (b), the light intensity (I) and initiator concentration (A0), but a steady state is independent of the light intensity (I). For the CE of FRP, the contribution from radical R had two cases: (i) linear dependence on T=bIA0, or (ii) nonlinear square root dependence T0.5. The synergistic effects led to higher conversion of FRP and CP, consistent with the measured results. The theoretically predicted new features include: (i) co-initiator [C] which always enhances both FRP and CP conversions, and (ii) co-initiator [B] which leads to more efficient FRP, but it also reduces CP.

Keywords

polymerization kinetics; photoinitiator; monomer conversion profile; synergistic effects

Subject

Chemistry and Materials Science, Applied Chemistry

Comments (1)

Comment 1
Received: 2 June 2022
Commenter: Jui-Teng Lin
Commenter's Conflict of Interests: Author
Comment: revision
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