The Trommsdorff effect under shear and bulk polymerization of methyl methacrylate via reactive extrusion

Zhan, Pengfei; Chen, Jianding; Zheng, Anna; Shi, Han; Chen, Fuxiu; Wei, Dafu; Xu, Xiang; Guan, Yong

doi:10.1016/j.eurpolymj.2019.109272

Cited by 15 publications

(17 citation statements)

References 33 publications

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“…Notably, the slopes of the exponential parts, once reached, are very similar for each subplot. Such variation is consistent with the starting of the gel effect during the polymerization [92,99].…”

Section: Case From Tablesupporting

confidence: 88%

“…It should be noted that the literature data are less clear in the overall framework of Figure 6, with e.g., a polymerization rate decrease with increasing shear rate [92], a molar mass build-up being hindered with increasing shear rate [101], and a viscosity build-up rate decrease with increasing shear rate [102]. The results in Figure 6 show that these observations are likely only true in certain reaction time regions, benefiting from the application of the developed protocol of Figure 2.…”

Section: Case From Tablementioning

confidence: 87%

“…Diffusivity codetermines the reaction rates [88,89], as it can hinder selectively the capacity of the molecules to move and come at a distance to effectively react. Diffusional limitations are significantly more relevant in the (homo)polymerization of MMA, as being the cause of a strong gel effect [26,[90][91][92][93], limiting the impact of the termination reaction and yielding an increase in the polymerization rate. Furthermore, reactivity ratios also determine which type of propagation reaction will be favored once the molecules are close enough to react.…”

Section: Analysis Of Gc Datamentioning

confidence: 99%

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Combining Chromatographic, Rheological, and Mechanical Analysis to Study the Manufacturing Potential of Acrylic Blends into Polyacrylic Casts

et al. 2021

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Polyacrylics have been considered for a broad range of material applications, including coatings, dental applications, and adhesives. In this experimental study, the casting potential of a group of (co)monomers belonging to the acrylic family has been explored to enable a more sustainable use of these polymer materials in the medical and veterinary science field. The individual contributions of each comonomer have been analyzed, the reaction conversion has been studied via gas chromatography (GC), the rheological behavior has been characterized via stress-controlled measurements, and the final mechanical properties have been obtained from tensile, flexure, and impact tests. The GC results allow assessing the pot life and thus the working window of the casting process. For the rheological measurements, which start from low-viscous mixtures, a novel protocol has been introduced to obtain accurate absolute data. The rheological data reflect the time dependencies of the GC data but facilitate a more direct link with the macroscopic material data. Specifically, the steep increase in the viscosity with increasing reaction time for the methyl methacrylate (MMA)/ethylene glycol dimethyl methacrylate (EGDMA) case (2% crosslinker) allows maximizing several mechanical properties: the tensile/flexure modulus, the tensile/flexure stress at break, and the impact strength. This opens the pathway to more dedicated chemistry design for corrosion casting and polyacrylic material design in general.

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Section: Case From Tablesupporting

confidence: 88%

Section: Case From Tablementioning

confidence: 87%

Section: Analysis Of Gc Datamentioning

confidence: 99%

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Combining Chromatographic, Rheological, and Mechanical Analysis to Study the Manufacturing Potential of Acrylic Blends into Polyacrylic Casts

et al. 2021

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“…[25] If not properly accounted for, the Trommsdorff effect can result in undesirable final material properties and/or reactor failure due to the exothermic nature of autoacceleration. Recently, Zhan and coworkers [26,27] have looked to take advantage of the Trommsdorff effect. They investigated the effect of shear rate on the Trommsdorff effect during the bulk polymerization of MMA and were able to use the results to produce PMMA with improved properties (compared to commercial PMMA) by using reactive extrusion techniques.…”

Section: Status Quo and Prospective Directions Autocatalysis In Kinetics Of Polymerization: Breakdown Of Equal Reactivity Hypothesismentioning

confidence: 99%

“…They investigated the effect of shear rate on the Trommsdorff effect during the bulk polymerization of MMA and were able to use the results to produce PMMA with improved properties (compared to commercial PMMA) by using reactive extrusion techniques. [26] The authors expanded on their previous work [26] to prepare methylmethacrylate-styrene copolymers in an inverted two-stage extruder by continuously feeding the co monomers into the extruder at the onset of the Trommsdorff effect to produce a copolymer with the desired physical properties. [27] Moving forward, experiments such as small-angle neutron scattering (SANS) and neutron spin echo coupled with new molecular theories could provide for a more complete picture of autoacceleration so that it might be used to improve industrial polymerization processes and material properties.…”

Section: Status Quo and Prospective Directions Autocatalysis In Kinetics Of Polymerization: Breakdown Of Equal Reactivity Hypothesismentioning

confidence: 99%

Harnessing autocatalytic reactions in polymerization and depolymerization

et al. 2021

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Autocatalysis and its relevance to various polymeric systems are discussed by taking inspiration from biology. A number of research directions related to synthesis, characterization, and multi-scale modeling are discussed in order to harness autocatalytic reactions in a useful manner for different applications ranging from chemical upcycling of polymers (depolymerization and reconstruction after depolymerization), self-generating micelles and vesicles, and polymer membranes. Overall, a concerted effort involving in situ experiments, multi-scale modeling, and machine learning algorithms is proposed to understand the mechanisms of physical and chemical autocatalysis. It is argued that a control of the autocatalytic behavior in polymeric systems can revolutionize areas such as kinetic control of the self-assembly of polymeric materials, synthesis of self-healing and self-immolative polymers, as next generation of materials for a sustainable circular economy. Graphic Abstract

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Thermoset polymers as host for optical limiting

Caillieaudeaux,

Muller,

Guerchoux

et al. 2023

J of Applied Polymer Sci

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The human eye, sensors, and photoreceptors can be damaged if they are submitted to laser beams with high intensities and low divergence. In the military field, an optical sensor can be damaged by pulsed laser radiations when exposed beyond its capacities. In order to have a protection against such threats, passive optical limiting is used. A mix between a reactive oligomer and a monomer, with methacrylate functions, is studied in the present work giving a thermoset matrix. To prevent the monomer evaporation, which results in the formation of bubbles in the final material, related to the reaction exotherm, an oligomer and a monomer with a high boiling temperature are used as precursors, giving a good alternative to a thermoplastic matrix like polymethyl methacrylate (PMMA). We report the experimental results of transient thermally induced optical nonlinearities (i.e., nonlinear refraction) in methacrylate‐based polymer filters at a nanosecond timescale, focus will be made to compare third order nonlinear refractive index from thermally induced refractive index. Optical filters are obtained by chemical bulk processes. In the present work, both thermoplastics and thermosets matrices were synthesized in order to characterize their optical limiting properties by mean of an appropriate custom‐made optical setup as well as their nonlinear refractive indices measured by the z‐scan technique. Optical measurements in the nonlinear regime are achieved at the wavelength of 1064 nm. To the best of the authors’ knowledge, such a work dealing on 3D‐network methacrylate‐based host has never been published.

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The Trommsdorff effect under shear and bulk polymerization of methyl methacrylate via reactive extrusion

Cited by 15 publications

References 33 publications

Combining Chromatographic, Rheological, and Mechanical Analysis to Study the Manufacturing Potential of Acrylic Blends into Polyacrylic Casts

Combining Chromatographic, Rheological, and Mechanical Analysis to Study the Manufacturing Potential of Acrylic Blends into Polyacrylic Casts

Harnessing autocatalytic reactions in polymerization and depolymerization

Thermoset polymers as host for optical limiting

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