Photoinitiating systems and kinetics of frontal photopolymerization processes – the prospects for efficient preparation of composites and thick 3D structures

Petko, Filip; Świeży, Andrzej; Ortyl, Joanna

doi:10.1039/d1py00596k

Cited by 46 publications

(35 citation statements)

References 136 publications

(218 reference statements)

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“…The major disadvantage of photo-FP is the need for continuous exposure of the reaction mixture to light radiation, where the rate and the degree of conversion depend on the given light intensity. However, as opposed to isothermal and thermal FP, the polymerization can be stopped at any time by simply “turning off the light” and can be reactivated when the light source is started [ 196 ].…”

Section: Frontal Polymerizationmentioning

confidence: 99%

A Review on Modeling Cure Kinetics and Mechanisms of Photopolymerization

et al. 2022

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Photopolymerizations, in which the initiation of a chemical-physical reaction occurs by the exposure of photosensitive monomers to a high-intensity light source, have become a well-accepted technology for manufacturing polymers. Providing significant advantages over thermal-initiated polymerizations, including fast and controllable reaction rates, as well as spatial and temporal control over the formation of material, this technology has found a large variety of industrial applications. The reaction mechanisms and kinetics are quite complex as the system moves quickly from a liquid monomer mixture to a solid polymer. Therefore, the study of curing kinetics is of utmost importance for industrial applications, providing both the understanding of the process development and the improvement of the quality of parts manufactured via photopolymerization. Consequently, this review aims at presenting the materials and curing chemistry of such ultrafast crosslinking polymerization reactions as well as the research efforts on theoretical models to reproduce cure kinetics and mechanisms for free-radical and cationic photopolymerizations including diffusion-controlled phenomena and oxygen inhibition reactions in free-radical systems.

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Section: Frontal Polymerizationmentioning

confidence: 99%

A Review on Modeling Cure Kinetics and Mechanisms of Photopolymerization

et al. 2022

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“…Four main ignition categories exist for frontal free-radical polymerizations: thermal, 29,33,44,46,50,67,75,76,78,[88][89][90]92,125,132,165,[198][199][200][201][202]205 photo, [55][56][57]133,165,250,252,254,[257][258][259][260][261][262][263][264] plasma, [265][266][267] and magnetocaloric. 201,234 Thermal triggering typically involves the use of a soldering iron or oil bath to heat a localized region.…”

Section: Ignition Techniquesmentioning

confidence: 99%

Frontal Polymerizations: From Chemical Perspectives to Macroscopic Properties and Applications

Suslick

Hemmer

Groce

et al. 2022

Preprint

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The synthesis and processing of thermoplastics and thermoset polymeric materials rely on energy-inefficient and environmentally burdensome manufacturing methods. Frontal polymerization has emerged as an attractive, scalable alternative due to its exploitation of the heat of polymerization, which generally is wasted as unutilized heat-loss. The only external energy needed for frontal polymerization is an initial thermal (or photo) stimulus that locally ignites the reaction. The subsequent reaction exothermicity provides local heating; the transport of this thermal energy to neighboring monomers in either a liquid or gel-like state results in a self-perpetuating reaction zone that provides fully-cured polymeric thermosets and thermoplastics. Propagation of this polymerization front continues through the unreacted monomer media until either all reactants are consumed or sufficient heat-loss stalls further reaction. Several different polymerization mechanisms support frontal processes, including free-radical, cat- or anionic, amine-cure epoxides, and ring-opening metathesis polymerization. The choice of monomer, initiator/catalyst, and additives dictates how fast the polymer front traverses the reactant medium, as well as the maximum temperature achievable. Frontal polymerization enables the preparation of moldable thermoplastics derived from linear polymers. When crosslinking is involved, polymeric networks (e.g., rigid thermosets) are obtainable through a related process best described as a frontal curing reaction. Numerous applications of frontally-generated polymers and thermosets exist, ranging from the reinforcement of porous substrates to the design of patterned composite materials. In this review, we examine in detail the physical and chemical phenomena that govern frontal polymerization, as well as outline the existing applications.

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“…[33] Recently, the development of energysaving, cheap and compact light sources with long-operating lifetimes have emerged on the market, namely light-emitting diodes. [34] Contrarily to UV light sources that were wellknown to release heat during operation, LEDs also enable to polymerize temperature-sensitive monomers. Replacement of UV light by visible light is also related to the higher light penetration which can be achieved in the visible range, as shown in the Figure 2.…”

Section: Introductionmentioning

confidence: 99%

Recent advances on carbazole-based oxime esters as photoinitiators of polymerization

Dumur

2022

European Polymer Journal

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Photoinitiating systems and kinetics of frontal photopolymerization processes – the prospects for efficient preparation of composites and thick 3D structures

Abstract: In recent years, frontal polymerisation has found a growing interest in many applications. Thus, its ability to cure thick samples with different fillers up to 50% by local application of...

Cited by 46 publications

References 136 publications

A Review on Modeling Cure Kinetics and Mechanisms of Photopolymerization

A Review on Modeling Cure Kinetics and Mechanisms of Photopolymerization

Frontal Polymerizations: From Chemical Perspectives to Macroscopic Properties and Applications

Recent advances on carbazole-based oxime esters as photoinitiators of polymerization

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