Preprint Article Version 1 Preserved in Portico This version is not peer-reviewed

Efficacy Analysis of Panchromatic New Copper Complex for Visible Light (455, 530 nm) Radical/Cationic Photopolymerization: The Synergic Effects and Catalytic Cycle

Version 1 : Received: 23 June 2021 / Approved: 23 June 2021 / Online: 23 June 2021 (12:37:02 CEST)

How to cite: Lin, J.; Lalevee, J.; Cheng, D. Efficacy Analysis of Panchromatic New Copper Complex for Visible Light (455, 530 nm) Radical/Cationic Photopolymerization: The Synergic Effects and Catalytic Cycle. Preprints 2021, 2021060582 (doi: 10.20944/preprints202106.0582.v1). Lin, J.; Lalevee, J.; Cheng, D. Efficacy Analysis of Panchromatic New Copper Complex for Visible Light (455, 530 nm) Radical/Cationic Photopolymerization: The Synergic Effects and Catalytic Cycle. Preprints 2021, 2021060582 (doi: 10.20944/preprints202106.0582.v1).

Abstract

. This article presents, for the first time, the kinetics and the general conversion features of a 3-component system (A/B/N), based on proposed mechanism of Mau et al, for both free radical polymerization (FRP) of acrylates and the free radical promoted cationic polymerization (CP) of epoxides using various new copper complex (G2) as the initiator. Higher FRP and CP conversion can be achieved by co-additive of [B] and N, via the dual function of (i) regeneration [A], and (ii) generation of extra radicals. The FRP and CP conversion efficacy (CE) are proportional to the nonlinear power of bI[A][B], where b and I are the effective absorption coefficient and the light intensity, respectively. In the interpenetrated polymer network (IPN) capable of initiating both FRP and CP in a blend of TMPTA and EPOX, (as the monomer for FRP and CP, respectively), the synergic effects due to CP include:: (i) CP can increase viscosity limiting the diffusional oxygen replenishment, such that oxygen inhibition effects are reduced; (ii) the cationic monomer also acts as a diluting agent for the IPN network , and (iii) the exothermic property of the CP. Many new findings are explored via our analytical formuals include: (i) the CE of FRP is about twice of the CE of CP, due to the extra radicals involved in FRP; (ii) the catalytic cycle enhancing the efficacy is mainly due to the regenaration of the initiator, and (iii) the nonlinear dependence of light intensity of the CE (in both FRP and CP). For the first time, the catalytic cycle, synergic effects, and the oxygen inhibition are theoretically confirmed to support the experimental hypothesis. The measured results of Mau et al are well analyzed and matching the predicted features of our modeling. .

Subject Areas

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

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