New multifunctional benzophenone-based photoinitiators with high migration stability and their applications in 3D printing

Liu, Shaohui; Brunel, Damien; Noirbent, Guillaume; Mau, Alexandre; Chen, Hong; Morlet‐Savary, Fabrice; Graff, Bernadette; Gigmès, Didier; Xiao, Pu; Dumur, Frédéric; Lalevée, Jacques

doi:10.1039/d0qm00885k

Cited by 48 publications

(44 citation statements)

References 32 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…these compounds could initiate the polymerization alone. We also reported that the 3-component (BT/Iod/Amine) PI system has higher conversion efficacy than that of 2-component (such as BT/Iod) [23]. This article will present, for the first time, the kinetics and the general conversion features of the 3-component (BT/Iod/Amine) PI system based on the proposed mechanism of Liu et al [22] for both FRP and CP.…”

Section: Introductionmentioning

confidence: 83%

“…Monomer M couples with radicals R and S (for FRP), and with couples with radical R' (for CP). A specific measured system of related to Figure 1 was reported by Liu et al [23], in which their Scheme 4 proposed a 3-component system of BT/Iod/EDB, where BT is benzophenonetriphenylamine photoinitiator, with Iod being the iodonium salt (oxidizing agent), and the amine EDB is ethyl 4-(dimethylamino)benzoate. Monomer rimethylolpropane triacrylate (TMPTA), and (3,4-epoxycyclohexane)methyl 3,4-epoxycyc-lohexylcarboxylate (EPOX) are teh functional groups for FRP and CP, respectively, via radicals of Ar* and EDB(-H)* (for FRP), and BT *+ (for CP).…”

Section: Photochemical Kineticsmentioning

confidence: 92%

“…Monomer rimethylolpropane triacrylate (TMPTA), and (3,4-epoxycyclohexane)methyl 3,4-epoxycyc-lohexylcarboxylate (EPOX) are teh functional groups for FRP and CP, respectively, via radicals of Ar* and EDB(-H)* (for FRP), and BT *+ (for CP). Various amine of BT1, BT2, BT3 and BT4 with different chemical and light absorptions are compared by Liu et al [23], which will be analyzed by the modeling based on Fig. 1.…”

Section: Photochemical Kineticsmentioning

confidence: 99%

“…More recently, we reported (for the first time) [23] the new initiator benzophenonetriphenylamine (BT), having the bifunctional and the trifunctional hybrid structures, not only strengthened thelight absorption, but also provided more active sites for the H-abstraction reaction in the presence of ethyl 4-(dimethylamino)benzoate (EDB). It could generate more free radical BT3-H*, in which more dissociative BT3-H* could be fixed via radical-radical self-coupling.…”

Section: Introductionmentioning

confidence: 99%

“…The key factors influencing the conversion rates and efficacy will be explored by analytic formulas derived from a kinetic model for a 3-component and 2-monomer system. Finally, the measured data of Liu et al [23] will be quantitatively analyzed by our formulas, rather than the qualitative discussions. Besides the general conversion features, new finding predicted by our analytic formulas will be explored.…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Efficacy Modeling of New Multi-Functional Benzophenone-Based System for Free-Radical/Cationic Hybrid Photopolymerization Using 405 nm LED

Lin¹,

Lalevée²

2021

Preprint

View full text Add to dashboard Cite

This article presents, for the first time, the kinetics and the general conversion features of a 3-component system, BT(BC)/iodonium/Amine, based on proposed mechanism of Liu et al, for both free radical polymerization (FRP) of acrylates and the free radical promoted cationic polymerization (CP) of epoxides using the new multi-functional initiator of benzophenone–triphenylamine (BT). The additives, iodonium and EDB, have the dual function of (i) regeneration BT and (ii) produce of extra radicals for improved FRP and CP. Analytic formulas are developed to explore the new features including: (i) the conversion efficacy (CE) of FRP is an increasing function of the light intensity, the effective absorption coefficient, and the concentration sum of each of the components, BT, Iod, amine, for transient state. However, CE at steady-state is independent to the light intensity; (ii) the trifunctional hybrid structures of BT3 leads to larger light absorption than other types of BT; it also provides more active sites for the H-abstraction in the presence of EDB, leading to high CE; (iii) the efficacy of FRP is an increasing function of the amine (EDB) concentration, in contrast to that of CP having an opposite dependence; (iv) the consumption rate of BT3 in the BT3/ Iod/EDB system is slower than that of the BT3/Iod system due to photoredox catalytic cycle, and the larger initiator regeneration (RGE) in the three-component system. A comprehensive model is also proposed that the CE (for both FRP and CP) is governed by (NjKjbI), whereas more complex formulas are developed; where Kj is an effective rate constant proportional to the electron transfer quantum yield, and the combined effects of other coupling rate constants; b is an effective absorption coefficient given by the light absorption and excited state quantum yield.

show abstract

Section: Introductionmentioning

confidence: 83%

Section: Photochemical Kineticsmentioning

confidence: 92%

Section: Photochemical Kineticsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Efficacy Modeling of New Multi-Functional Benzophenone-Based System for Free-Radical/Cationic Hybrid Photopolymerization Using 405 nm LED

Lin¹,

Lalevée²

2021

Preprint

View full text Add to dashboard Cite

show abstract

Photopolymerization Approach to Advanced Polymer Composites: Integration of Surface‐Modified Nanofillers for Enhanced Properties

Peng,

Zhang,

Xiao

2024

Advanced Materials

View full text Add to dashboard Cite

The incorporation of functionalized nanofillers into polymers via photopolymerization approach has gained significant attention in recent years due to the unique properties of the resulting composite materials. Surface modification of nanofillers plays a crucial role in their compatibility and polymerization behavior within the polymer matrix during photopolymerization. This review focuses on the recent developments in surface modification of various nanofillers, enabling their integration into polymer systems through photopolymerization. The article discusses the key aspects of surface modification of nanofillers, including the selection of suitable surface modifiers, such as photoinitiators and polymerizable groups, as well as the optimization of modification conditions to achieve desired surface properties. The influence of surface modification on the interfacial interactions between nanofillers and the polymer matrix is also explored, as it directly impacts the final properties of the nanocomposites. Furthermore, the review highlights the applications of nanocomposites prepared by photopolymerization, such as sensors, gas separation membranes, purification systems, optical devices, and biomedical materials. By providing a comprehensive overview of the surface modification strategies and their impact on the photopolymerization process and the resulting nanocomposite properties, this review aims to inspire new research directions and innovative ideas in the development of high‐performance polymer nanocomposites for diverse applications.This article is protected by copyright. All rights reserved

show abstract

Photopolymerization of Zeolite Filler‐Based Composites for Potential 3D Printing Application and Gas Adsorption Applications

Zhang

Gao

Josien

et al. 2021

Adv Materials Technologies

Self Cite

View full text Add to dashboard Cite

In recent years, photopolymerization has been found wide applications in industry and daily life, while many defective properties of polymers limit their development, including compressive strength, mechanical properties and functions. Furthermore, zeolites are microporous solids with many industrial applications.As fillers they can improve mechanical properties of zeolite/polymer composite and transfer their properties to composites. Here we reported the fabrication of composites with very high filler contents (80-95 wt%) under mild photopolymerization conditions (visible LED light irradiation, room temperature, under air). Compared to pure poly(ethylene glycol) diacrylate (PEGDA) polymer, mechanical properties have been greatly improved, and the storage modulus increased by nearly 20-fold compared to that of pure polymer. After debinding/sintering of composites by high temperature treatment, zeolite porosity is preserved with good adsorption capacities. Some step-like object with 3D structure was also obtained by an original 3D printing technique noted "layer by layer Molding/Curing". Hence, as a great breakthrough, this work is expected to lead to a valuable development in the field of photopolymerization in quite highly filled composites. This also will expand their potential applications for 3D printing in the fields of high-performance lightweight materials and adsorption, and opens the door to a new process of zeolite shaping.

show abstract

New multifunctional benzophenone-based photoinitiators with high migration stability and their applications in 3D printing

Abstract: A series of photoinitiators based on benzophenone scaffold are developed for LED photopolymerization. Excellent photoinitiation abilities are obtained and 3D printing experiments are carried out successfully.

Cited by 48 publications

References 32 publications

Efficacy Modeling of New Multi-Functional Benzophenone-Based System for Free-Radical/Cationic Hybrid Photopolymerization Using 405 nm LED

Efficacy Modeling of New Multi-Functional Benzophenone-Based System for Free-Radical/Cationic Hybrid Photopolymerization Using 405 nm LED

Photopolymerization Approach to Advanced Polymer Composites: Integration of Surface‐Modified Nanofillers for Enhanced Properties

Photopolymerization of Zeolite Filler‐Based Composites for Potential 3D Printing Application and Gas Adsorption Applications

Contact Info

Product

Resources

About