Synthesis and characterization of nanocomposites with nanocellulose obtained through frontal polymerization and study of their properties

Arellano-Cruz, Dulce Cristel; Illescas, Javier; Martínez-Gallegos, Sonia; Díaz-Nava, María del Carmen

doi:10.1557/s43580-021-00169-z

Cited by 4 publications

(13 citation statements)

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“…Free-radical polymerizations are the most common type of frontal systems, with over 80 published reports as of 2022 (refs , , , , − , , − , , − , , − , , , , , , − ). Three distinct mechanistic regimes exist for chain growth radical polymerizations (see the simplified Scheme ).…”

Section: Chemistries Of Existing Frontal Polymerization Systemsmentioning

confidence: 99%

Frontal Polymerizations: From Chemical Perspectives to Macroscopic Properties and Applications

et al. 2023

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The synthesis and processing of most thermoplastics and thermoset polymeric materials rely on energy-inefficient and environmentally burdensome manufacturing methods. Frontal polymerization is an attractive, scalable alternative due to its exploitation of polymerization heat that is generally wasted and unutilized. 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 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. Numerous applications of frontally generated materials exist, ranging from porous substrate reinforcement to fabrication of patterned composites. 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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Section: Chemistries Of Existing Frontal Polymerization Systemsmentioning

confidence: 99%

Frontal Polymerizations: From Chemical Perspectives to Macroscopic Properties and Applications

et al. 2023

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“…The majority of published reports employ frontal free-radical polymerization. 29,33,34,[44][45][46][47][48]50,[57][58][59][60]67,[74][75][76]78,[81][82][83][84][85][86][87][88][89][90]92,112,125,132,194,[244][245][246][247][248][249]251,252 The addition of a thermal radical source induces a series of radical chain reactions of acrylate or acrylamide derived monomers. The nature of the initiator dictates several key features.…”

Section: Large-scale Fabrication and 3d-printingmentioning

confidence: 99%

“…As with cationic epoxy FP, a large number of composite materials derived from radical FP exist. 33,50,81,85,125,205,208,230,237,240,241,245,246,265,295 Two studies by Viner and Viner 125,230 investigated the effects of fillers for frontal cyanate ester polymerizations. The base formulation in these studies consisted of TMPTA and Luperox-231 (10.4 phr).…”

Section: Fillers and Additivesmentioning

confidence: 99%

“…159 Similarly, frontally derived composite materials that contain biopolymeric fillers exist. 245,246 Early work from Mariani and coworkers 159 demonstrated that two modes of FP (radical and FROMP) occur simultaneously in mixtures of MMA, DCPD, and G1 with either BPO or AIBN. One may view the p(DCPD) interpenetrating network as an organic filler, though the mechanical and thermochemical properties of such polymers remain unexplored.…”

Section: Fillers and Additivesmentioning

confidence: 99%

“…Several appealing uses of these stimuli-responsive polymers exist, ranging from heavy metal ion removal 228,231,[258][259][260][261] to controlled drug delivery 88,203,232,303 or chemical detection. 207,234,262 Besides hydrogel generation, functionally gradient polymers 147,199,216 and composite materials 32,44,48,50,61,66,74,205,229,233,245,246,248,257,263,[265][266][267]295 are easily obtained via FP. Successful reactivity within a semi-porous substrate (e.g., wood, stone), for example, provides structural reinforcement, which has direct implications for consolidation and conservation purposes.…”

Section: Large-scale Fabrication and 3d-printingmentioning

confidence: 99%

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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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Frontal Polymerization for the Rapid Obtainment of Polymer Composites

Malucelli,

Mariani

2024

ACS Omega

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Among the different polymerization techniques, frontal polymerization (FP) has gained high interest from the scientific community because of its peculiar characteristics: in particular, compared to classic polymerization reactions, FP allows for a better exploitation of the heat of polymerization involved, without requiring any external energy input apart from an initial photo or thermal ignition that triggers the reaction. The latter usually propagates in a few tenths of seconds or (at most) minutes through a hot self-sustaining polymerization front, giving rise to the formation of fully cured thermosetting networks or thermoplastic polymers. Furthermore, different polymerization mechanisms can be involved in FP reactions, comprising cationic or anionic, ring-opening metathesis, and free-radical polymerization, among others. Further, it is possible to run FP reactions in bulk, in solution, or even using solid monomers if they are melted at the temperature of the front, notwithstanding the possibility of using reactive systems containing fillers or fiber/fabric reinforcements. In this context, the use of FP is becoming very important also for the design and production of advanced (nano)composite materials, saving processing time and achieving the completeness of the curing reaction, even in the presence of high filler/reinforcement loadings. Therefore, this mini-review aims to provide the reader with the basics of FP and its main peculiarities, even in the context of preparing highperforming composites. In this respect, some recent case studies witnessing the potentialities of frontal polymerization for the design of advanced (nano)composite systems will be elucidated. Finally, some perspectives about possible future developments will be proposed.

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Synthesis and characterization of nanocomposites with nanocellulose obtained through frontal polymerization and study of their properties

Cited by 4 publications

References 10 publications

Frontal Polymerizations: From Chemical Perspectives to Macroscopic Properties and Applications

Frontal Polymerizations: From Chemical Perspectives to Macroscopic Properties and Applications

Frontal Polymerizations: From Chemical Perspectives to Macroscopic Properties and Applications

Frontal Polymerization for the Rapid Obtainment of Polymer Composites

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