Unveiling the reactivity of epoxides in carbonated epoxidized soybean oil and application in the stepwise synthesis of hybrid poly(hydroxyurethane) thermosets

Cramail, Henri; Helbling, P.; Tassaing, Thierry; Vidil, Thomas; Hermant, F.; Petit, M.

doi:10.1039/d2py01318e

Cited by 17 publications

(10 citation statements)

References 51 publications

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“…We identified epoxides as ideal candidates since their aminolysis is known to create an important exotherm , that is correlated to the strain release of the cycle, further enhanced in epoxy resins by the rapid viscosity increase preventing efficient heat dissipation. Moreover, these precursors are compatible with the PHU chemistry, yet keeping the foaming process very simple while affording PHU/epoxide hybrids known to be robust materials with enhanced properties. − For the proof of concept, F3 was modified by partly substituting TMPTC by its epoxy precursor, i.e., trimethylolpropane triglycidyl ether (TMPTE) (Figure A,B; see Section 2 in the Supporting Information for details). The red curve in Figure A shows that epoxides and cyclic carbonates teamed up to significantly increase the reaction exotherm.…”

Section: Resultsmentioning

confidence: 99%

Cascade Exotherms for Rapidly Producing Hybrid Nonisocyanate Polyurethane Foams from Room Temperature Formulations

Bourguignon,

Grignard,

Detrembleur

2023

J. Am. Chem. Soc.

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For decades, self-blown polyurethane foams�found in an impressive range of materials�are produced by the toxic isocyanate chemistry and are difficult to recycle. Producing them in existing production plants by a rapid isocyanate-free self-blowing process from room temperature (RT) formulations is a long-lasting challenge. The recent water-induced self-blowing of nonisocyanate polyurethane (NIPU) formulations composed of a CO 2 -based tricyclic carbonate, diamine, water, and a catalyst successfully addressed the isocyanate issue, however failed to provide foams at RT. Herein, we elaborate a practical solution to empower the NIPU foam formation in record timeframes from RT formulations. We generate cascade exotherms by the addition of a highly reactive triamine and an epoxide to the formulation of the water-induced self-foaming process. These exotherms, combined to a fast cross-linking imparted by the triamine and epoxide, rapidly raise the temperature to the foaming threshold and deliver hybrid NIPU foams in 5 min with KOH as a catalyst. Careful selection of the monomers enables producing foams with a wide range of properties, as well as with an unprecedented high biobased content up to 90 wt %. Moreover, foams can be upcycled into polymer films by hot pressing, offering them a facile reuse scenario. This robust cheap process opens huge perspectives for greener foams of high biobased contents, expectedly responding to the sustainability demands of the foam sector. It is potentially compatible to the retrofitting of industrial foaming infrastructures, which is of paramount importance to accommodate existing foam production plants and address the huge foam market demands.

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Section: Resultsmentioning

confidence: 99%

Cascade Exotherms for Rapidly Producing Hybrid Nonisocyanate Polyurethane Foams from Room Temperature Formulations

Bourguignon,

Grignard,

Detrembleur

2023

J. Am. Chem. Soc.

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“…b) Partial carbonations of vegetable oils leading to PCVOs and c) their use for the synthesis of PHUs such as CSBO45 and HDA‐PCLSO (the partial opening and crosslinking of the epoxide moieties is not shown). [ 269‐270 ] d) Treatment of PCVOs with H 2 O or EtOH to afford ROPCVOs [ 269 ] as precursors of PHUs by e) reaction with diamines. f) Post‐synthetic modification of PHU‐T with epichlorohydrin to afford PHU‐Az .…”

Section: Overview Of Multi‐5ccsmentioning

confidence: 99%

“…In a subsequent work, Cramail et al . [ 269 ] carried out a systematic kinetic investigation of the reactivity of diamines with epoxides or 5CC groups of PCVOs . The authors carried out the partial carbonation of CSBO (leading to PCSBO ) by varying the duration of cycloaddition reaction of CO 2 to the epoxidized SBO precursor ( ESBO ).…”

Section: Overview Of Multi‐5ccsmentioning

confidence: 99%

Polyhydroxyurethanes from Biobased Monomers and CO₂: A Bridge between Sustainable Chemistry and CO₂ Utilization^†

Theerathanagorn,

Kessaratikoon,

Rehman

et al. 2023

Chin. J. Chem.

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Comprehensive SummaryPolyhydroxyurethanes (PHUs) have received considerable attention in the last decade as potential alternatives to traditional phosgene‐based polyurethanes (PUs). The development of suitable 5CC (five membered‐ring cyclic carbonate) precursors bearing multiple carbonate moieties (multi‐5CCs) is a key requisite for preparing PHUs by polyaddition reaction with bis‐ or polyamines. Producing sustainable PHUs from CO2‐based five‐membered cyclic carbonates (5CCs) obtained from biobased epoxides is a valuable strategy to bridge CO2 utilization and the upcycling of renewable substrates. In this context, while many multi‐5CC monomers reported in the literature are oil‐based, recent efforts have led to the development of a large variety of multifunctional 5CCs that are produced by the combination of CO2 and renewable resources such as fatty acids and vegetable oils, lignin, terpenes, and sugars. In this work, recent crucial advances (2019—2023) on PHUs prepared from bis‐ and multi‐5CCs produced from CO2 and (partially/potentially) biobased substrates are reviewed with respect to their synthesis, thermal and mechanical properties, and their recent, emerging applications.

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“…Recently, Helbling et al further investigated the relative reactivity of carbonates and esters, but also of epoxides, by studying the crosslinking reaction of a partially carbonated ESBO with different diamines. [ 104 ] Dual‐spectroscopic monitoring (infrared and Raman) indicates that cyclic carbonates are more reactive than epoxides, the latter being more reactive than esters. Based on this comprehensive knowledge of the functions reactivity, the authors demonstrate that the extent of ester aminolysis can be minimized by using a two‐stage curing schedule with a first step at 80 °C for 1 h and a second step at 120 °C for 5 h. Figure a represents the conversion of the different moieties as a function of time for the two‐stage curing schedule while Figure 18b represents the same conversion profiles for a one‐step curing schedule at 120 °C for 6 h. Clearly, the final ester conversion is about 20% in the first case against 30% in the latter case.…”

Section: Synthesis Of Thermosetting Phus: High‐ Versus Low‐temperatur...mentioning

confidence: 99%

Design of Plurifunctional Cyclocarbonates and their Use as Precursors of Poly(hydroxyurethane) Thermosets: A Review

Helbling,

Hermant,

Petit

et al. 2023

Macro Chemistry & Physics

Self Cite

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Polyhydroxyurethanes (PHUs) are promising polymers to replace polyurethanes (PUs), classically obtained by the isocyanate‐alcohol route. Various application fields of PUs, e.g. foams or coatings, require the use of thermosetting polymers. Hence, a great deal of effort has been devoted to the development of PHU thermosets in the recent literature. This review highlights the different strategies developed through the years to synthesize plurifunctional cyclic carbonates, also called poly(cyclic carbonate)s, and whose functionality ≥ 3 is a prerequisite for the synthesis of thermosetting PHUs. A special emphasize is accorded to the safe and eco‐friendly synthetic approaches (e.g., phosgene‐free, use of renewable reactants). In addition, the curing strategies implemented to overcome the low reactivity of the monomers and the limitations related to the transitions of the growing networks (i.e., viscosification, gelation, vitrification) are described. In the end, the curing of PHUs under mild thermal conditions, down to room temperature, is described. Such curing conditions are uncommon for PHU thermosets and are paving the way to much anticipated applications such as coatings, adhesives or 3D‐printing.This article is protected by copyright. All rights reserved

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Unveiling the reactivity of epoxides in carbonated epoxidized soybean oil and application in the stepwise synthesis of hybrid poly(hydroxyurethane) thermosets

Abstract: In this work, the crosslinking reaction of partially carbonated epoxidized soybean oils with different diamines was investigated. To this end, a series of carbonated soybean oils (CSBO), with a carbonation...

Cited by 17 publications

References 51 publications

Cascade Exotherms for Rapidly Producing Hybrid Nonisocyanate Polyurethane Foams from Room Temperature Formulations

Cascade Exotherms for Rapidly Producing Hybrid Nonisocyanate Polyurethane Foams from Room Temperature Formulations

Polyhydroxyurethanes from Biobased Monomers and CO₂: A Bridge between Sustainable Chemistry and CO₂ Utilization^†

Design of Plurifunctional Cyclocarbonates and their Use as Precursors of Poly(hydroxyurethane) Thermosets: A Review

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Unveiling the reactivity of epoxides in carbonated epoxidized soybean oil and application in the stepwise synthesis of hybrid poly(hydroxyurethane) thermosets

Abstract: In this work, the crosslinking reaction of partially carbonated epoxidized soybean oils with different diamines was investigated. To this end, a series of carbonated soybean oils (CSBO), with a carbonation...

Cited by 17 publications

References 51 publications

Cascade Exotherms for Rapidly Producing Hybrid Nonisocyanate Polyurethane Foams from Room Temperature Formulations

Cascade Exotherms for Rapidly Producing Hybrid Nonisocyanate Polyurethane Foams from Room Temperature Formulations

Polyhydroxyurethanes from Biobased Monomers and CO2: A Bridge between Sustainable Chemistry and CO2 Utilization†

Design of Plurifunctional Cyclocarbonates and their Use as Precursors of Poly(hydroxyurethane) Thermosets: A Review

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Product

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Polyhydroxyurethanes from Biobased Monomers and CO₂: A Bridge between Sustainable Chemistry and CO₂ Utilization^†