Synthesis of polyester thermosets via internally catalyzed Michael-addition of methylene compounds on a 2-(trifluoromethyl)acrylate-derived building block

Berne, Dimitri; Caillol, Sylvain; Ladmiral, Vincent; Leclerc, E.

doi:10.1016/j.eurpolymj.2022.111362

Cited by 1 publication

(3 citation statements)

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“…First, a trifunctional (trifluoromethyl)acrylate incorporating a tertiary amine (NMAF 3 ) was synthesized from triethanolamine as previously reported. 68 Reacting NMAF 3 with 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 2,2′-(ethylenedioxy)diethanethiol, pentaerythritol tetrakis(3-mercaptopropionate) and 4,4′-thiobisbenzenethiol, led to the corresponding thia-Michael CANs (TMCANs): Prop-, But-, Pent-, Hex-, EDT-, PETMP-and TBT-TMCAN, respectively (Figure 3). This network formation reaction was carried out in solution (50 wt % in DCM) as the thia-Michael addition was extremely fast and exothermic at 25 °C in the absence of solvent.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Once the dynamic character of the thia-Michael adduct under dual activation by fluorine and tertiary amine was demonstrated, seven CANs based on this exchangeable bond were synthesized. First, a trifunctional (trifluoromethyl)acrylate incorporating a tertiary amine ( NMAF 3 ) was synthesized from triethanolamine as previously reported . Reacting NMAF 3 with 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 2,2′-(ethylenedioxy)diethanethiol, pentaerythritol tetrakis(3-mercaptopropionate) and 4,4′-thiobisbenzenethiol, led to the corresponding thia-Michael CANs ( TMCANs ): Prop- , But- , Pent- , Hex- , EDT- , PETMP- and TBT-TMCAN , respectively (Figure ).…”

Section: Resultsmentioning

confidence: 99%

“…In the past few years, our group has evidenced the significant activating effect of fluorine for the synthesis of a range of polymer networks. In particular, thanks to its high electronegativity, epoxy/acid, , amidation, and Michael additions (including the aza and thia versions) − have been shown to be strongly accelerated by proximal fluorine atom substitution. Moreover, fluorine activation not only enables the fast synthesis of these networks but also promotes a series of exchange reactions.…”

Section: Introductionmentioning

confidence: 99%

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Combination of Fluorine and Tertiary Amine Activation in Catalyst-Free Thia-Michael Covalent Adaptable Networks

Berne,

Poli,

Caillol

et al. 2023

Macromolecules

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A series of catalyst-free covalent adaptable networks (CANs) have been developed using a reversible thia-Michael reaction activated by fluorine atom substitution and by an intramolecular tertiary amine. The thia-Michael exchange rate was first evaluated by a preliminary molecular study coupled to density functional theory (DFT) calculations. This study enabled us to highlight the necessity of combining fluorine and tertiary amine activation to observe the thia-Michael exchange. Then, by modulating the structure, nature, and functionality of the thiol monomers, a wide range of mechanical properties and thermal properties were achieved. Relationships between the monomer structure and the dynamic properties were also highlighted through the dynamic study of these materials. Finally, the ability of the fluorinated thia-Michael CANs to be reprocessed was assessed by thermal and mechanical analyses of up to three reshaping cycles.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%