Frontal Polymerization

Pojman, John A.

doi:10.1002/9783527632602.ch4

Cited by 17 publications

(14 citation statements)

References 89 publications

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“…Such nonplanar modes of propagation have been the subject of much investigation. 40,[45][46][47][48][49][50][51] The complexity of the front increases with the value of the effective energy of activation. By reducing the number of propagating radicals, the transition metal reduces the contribution of the energy of activation for the termination step, which increases the effective activation energy.…”

Section: Resultsmentioning

confidence: 99%

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Thermal frontal polymerization with a thermally released redox catalyst

Parrinello

Bounds

Liveri

2012

J. Polym. Sci. A Polym. Chem.

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We studied thermal frontal polymerization using a redox system in an attempt to lower the temperature of the frontally polymerizable system while increasing the front velocity so as to obtain a self-sustaining front in a thinner layer than without the redox components. A cobalt-containing polymer with a melting point of 63 C (Intelimer 6050X11) and cumene hydroperoxide were used with a triacrylate. The use of the Intelimer decreased the front velocity but allowed fronts to propagate in thinner layers and with more filler while still having a pot life of days. Nonplanar modes of propagation occurred. Fronts propagated faster when 6-O-palmitoyl-L-ascorbic acid was used as a reductant. Interestingly, fronts were also faster with the reductant even without the Intelimer if kaolin clay was the filler; however, the pot life was significantly reduced.

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Section: Resultsmentioning

confidence: 99%

“…Achieving this goal might allow adhesives and coatings based on frontal polymerization. 40 The cobalt used in this research was contained in the polymer, Intelimer 6050X11. The cobalt is encapsulated within an Intelimer polymer, which is synthesized to have crystalline side chains in which cobalt-containing moieties are trapped.…”

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confidence: 99%

Thermal frontal polymerization with a thermally released redox catalyst

Parrinello

Bounds

Liveri

2012

J. Polym. Sci. A Polym. Chem.

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“…2). 5,6 The initiation process of the FP can be started either by irradiation with light or by local application of heat. However a front can only be sustained if the heat loss is low enough, so that enough energy is available to cleave further initiators.…”

Section: Introductionmentioning

confidence: 99%

Successful radical induced cationic frontal polymerization of epoxy-based monomers by C–C labile compounds

2015

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Thermal bulk curing of epoxy resins is a non-energy efficient method. On the other hand classical photocuring techniques for epoxy resins are limited to quite thin layers, due to the limited penetration depth of UV-light. We show that Radical Induced Cationic Frontal Polymerization (RICFP) is a promising technique for the energy efficient bulk curing of epoxy resins. The combination of a C-C labile compound (1,1,2,2tetraphenylethanediol) as a thermal radical initiator with diaryliodonium salts results upon local thermalor photoinitiation in a self-sustaining front moving along the formulation and curing cationically curable resins completely. This allows the curing of monomer formulations in places that are not easily accessible or on objects that cannot be thermally cured because of their thermal instability or size. In this paper we report about first basic investigations on RICFP of several epoxy resins with C-C-labile compounds and compare them to common thermal radical initiators. Fig. 1 Structure of the bisphenol A diglycidylether resin (BADGE). † Electronic supplementary information (ESI) available. See

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“…In particular, under conditions of strong light attenuation and limited mass and thermal diffusion, a sharp monomer‐to‐polymer conversion profile develops and propagates as a planar front normal to the illuminated surface. This light‐driven process is referred to as frontal photopolymerization (FPP), and shares a number of features with autocatalytic frontal polymerization . However, the FPP process can generally be started and stopped by switching on or off the light source and thus, from a manufacturing perspective, FPP offers an attractive and precise means of thickness control in both unbounded and 3D photopolymerization.…”

Section: Introductionmentioning

confidence: 99%

Coarse‐grained models for frontal photopolymerization with evolving conversion profile

Purnama

Hennessy

Vitale

et al. 2017

Polymer International

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We introduce a series of ‘minimal’ models to describe a common light-driven directional solidification process, known as frontal photopolymerization (FPP), focusing on experimental observables: the solidification kinetics, light attenuation and spatiotemporal monomer-to-polymer conversion. Specifically, we focus on FPP propagation that yields conversion profiles that are not invariant with time, and which cannot be simply described by the presence of mass or heat diffusion. The models are assessed against experimental data for the photopolymerization of a model trimethacrylate system. We find that the simplest model, comprising a single equation of motion for the conversion fraction ϕ and a generalized Beer–Lambert law, can only describe the experimental data by assuming an unphysical variation in optical absorption. Introducing a ϕ-dependent reaction constant Keff is found to require a time dependence, regardless of the functional form in ϕ. We conclude by introducing a ‘minimal’ chemical model, which is based on a simple three-step reaction scheme involving the spatiotemporal evolution of the photoinitiator fraction, relative fraction of radicals and monomer conversion fraction, that is able to capture the experimental data with a small number of parameters and under reasonable FPP assumptions. Our framework provides important predictive ability for ubiquitous solidification and patterning processes, including three-dimensional printing, via photopolymerization

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Frontal Polymerization

Cited by 17 publications

References 89 publications

Thermal frontal polymerization with a thermally released redox catalyst

Thermal frontal polymerization with a thermally released redox catalyst

Successful radical induced cationic frontal polymerization of epoxy-based monomers by C–C labile compounds

Coarse‐grained models for frontal photopolymerization with evolving conversion profile

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