Facile construction of functional poly(monothiocarbonate) copolymers under mild operating conditions

Habets, Thomas; Siragusa, Fabiana; Müller, Alejandro J.; Grossman, Quentin; Ruffoni, Davide; Grignard, Bruno; Detrembleur, Christophe

doi:10.1039/d2py00307d

Cited by 12 publications

(32 citation statements)

References 33 publications

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“…The DSC analysis revealed the presence of two glass-transition temperatures ( T g ) at 64 and 124 °C. This unusual thermal behavior was recently observed by our group for other types of poly(hydroxy-oxazolidone)-containing copolymers, i.e., poly(thiocarbonate- co -hydroxy-oxazolidinone)s obtained by the terpolymerization of BisαCC with dithiols and diamines . We hypothesized that the first T g corresponds to the main glassy matrix, while the second T g might be related to the presence of hydrogen bonding between the hydroxy-oxazolidinone linkages, leading to a minor glassy phase.…”

Section: Resultsmentioning

confidence: 99%

“…This unusual thermal behavior was recently observed by our group for other types of poly(hydroxy-oxazolidone)-containing copolymers, i.e., poly-(thiocarbonate-co-hydroxy-oxazolidinone)s obtained by the terpolymerization of BisαCC with dithiols and diamines. 46 We hypothesized that the first T g corresponds to the main glassy matrix, while the second T g might be related to the presence of hydrogen bonding between the hydroxy-oxazolidinone linkages, leading to a minor glassy phase. Further investigations would however be needed to fully explain this unusual but reproducible thermal behavior, which is out of the scope of this paper.…”

Section: Acs Sustainablementioning

confidence: 99%

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Catalyst-Free Approach for the Degradation of Bio- and CO₂-Sourced Polycarbonates: A Step toward a Circular Plastic Economy

Siragusa

Habets

Méreau

et al. 2022

ACS Sustainable Chem. Eng.

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Designing easily degradable polymers has become a new challenge to overcome the post-consumer plastic waste accumulation in the environment. Polycarbonates are important polymers that can be chemically recycled; however, most often, their degradation requires high temperatures and/or the use of catalysts. In this work, we report the facile chemical recycling of regioregular polycarbonates prepared by the organocatalyzed copolymerization of CO2-sourced exovinylene biscyclic carbonates (BisαCC) with diols derived from biomass. These polymers, thanks to their pending ketone groups, are rapidly (<30 min) and totally deconstructed into the parent diol and a bis(oxazolidinone) by catalyst-free aminolysis at 25 °C. By using 3-propanolamine for the aminolysis, a hydroxy-functionalized bis(oxazolidinone) is recovered, which can be copolymerized with BisαCC to yield a polymer alternating carbonate and oxazolidinone linkages. Importantly, the same bis(oxazolidinone) scaffold is recovered as the main product by aminolysis of this copolymer, offering a close-loop recycling scenario for this polymer. This work illustrates that these polycarbonates are prone to facile and complete aminolysis under mild and catalyst-free conditions, but can also be exploited to prepare new building blocks for the synthesis of novel degradable polymers. The mechanism of formation of these heterocycles is studied by model reactions and rationalized by density functional theory (DFT) calculations.

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Section: Resultsmentioning

confidence: 99%

Section: Acs Sustainablementioning

confidence: 99%

Catalyst-Free Approach for the Degradation of Bio- and CO₂-Sourced Polycarbonates: A Step toward a Circular Plastic Economy

Siragusa

Habets

Méreau

et al. 2022

ACS Sustainable Chem. Eng.

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“…Having established that SGs improve solution-state characterization of PHO, we then investigated the effect of these groups on POxa. PHO with alkyl SGs were readily dehydrated to form POxa at room temperature using catalytic acid (Table ), improving upon reported conditions that required high temperature, excess acid, or both. , Because of changes in solubility following dehydration ( vide infra ), POxa molar masses ( M n = 2.8–8.3 kDa) were determined in CHCl 3 using polystyrene (PS) standards. Therefore, these values could not be directly compared to the PHO precursors.…”

Section: Results and Discussionmentioning

confidence: 99%

Improved Characterization of Polyoxazolidinones by Incorporating Solubilizing Side Chains

et al. 2022

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Carbon dioxide-based polyoxazolidinones (POxa) are an emerging subclass of non-isocyanate polyurethanes for high temperature applications. Current POxa with rigid linkers suffer from limited solubility that hinders synthesis and characterization. Herein, we report the addition of alkyl and alkoxy solubilizing groups to rigid spirocyclic POxa and their poly(hydroxyoxazolidinone) (PHO) precursors. The modified polymers were soluble in up to six organic solvents, enabling characterization of key properties (e.g., molar mass and polymer structure) using solution-state methods. Dehydration of PHO to POxa changed solubility from highly polar to less polar solvents and improved thermal stability by 76−102 °C. The POxa had relatively high glass transition (85−119 °C) and melting (190−238 °C) temperatures tuned by solubilizing group structure. The improved understanding of factors affecting solubility, structure−property relationships, and degradation pathways gained in this study broadens the scope of soluble POxa and enables more rational design of this promising class of materials.

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“…We then investigated the lower thermal stability of PHO compared to POxa using TGA-mass spectrometry (TGA-MS). TGA-MS analysis of C3 PHO (Figures S22-24) supported the occurrence of multiple degradation pathways, including partial dehydration to POxa 11,45 and reversion to oxourethanes (Scheme 3). The oxourethane structure is an intermediate in PHO synthesis (Scheme S1) 11,25 and contains acyclic urethanes with lower thermal stability than the corresponding cyclic oxazolidinones.…”

Section: Polymer Synthesis and Structural Characterizationmentioning

confidence: 86%

“…PHO with alkyl SGs were readily dehydrated to form POxa at room temperature using catalytic acid (Table 2), improving upon reported conditions that required high temperature, excess acid, or both. 11,45 Due to changes in solubility following dehydration (vide infra), POxa molar masses (Mn = 2.8-8.3 kDa) were determined in CHCl3 using polystyrene (PS) standards. Therefore, these values could not be directly compared to the PHO precursors.…”

Section: Polymer Synthesis and Structural Characterizationmentioning

confidence: 99%

Improved Characterization of Polyoxazolidinones by Incorporating Solubilizing Side Chains

Wong

Barrera

Pal

et al. 2022

Preprint

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Carbon dioxide-based polyoxazolidinones (POxa) are an emerging subclass of non-isocyanate polyurethanes for high temperature applications. Current POxa with rigid linkers suffer from limited solubility that hinders synthesis and characterization. Herein, we report the addition of alkyl and alkoxy solubilizing groups to rigid spirocyclic POxa and their poly(hydroxyoxazolidinone) (PHO) precursors. The modified polymers were soluble in up to 6 organic solvents, enabling characterization of key properties (i.e., molar mass and polymer structure) using solution-state methods. Dehydration of PHO to POxa changed solubility from highly polar to less polar solvents and improved thermal stability by 76–102 °C. The POxa had relatively high glass transition (85–119 °C) and melting (190–238 °C) temperatures tuned by solubilizing group structure. The improved understanding of factors affecting solubility, structure-property relationships, and degradation pathways gained in this study broadens the scope of soluble POxa and enables more rational design of this promising class of materials.

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Facile construction of functional poly(monothiocarbonate) copolymers under mild operating conditions

Abstract: The installation of both oxazolidone and thiocarbonate linkages within a single polymer backbone remains elusive by simple procedures under mild conditions. In this work, we report the construction of copolymers...

Cited by 12 publications

References 33 publications

Catalyst-Free Approach for the Degradation of Bio- and CO₂-Sourced Polycarbonates: A Step toward a Circular Plastic Economy

Catalyst-Free Approach for the Degradation of Bio- and CO₂-Sourced Polycarbonates: A Step toward a Circular Plastic Economy

Improved Characterization of Polyoxazolidinones by Incorporating Solubilizing Side Chains

Improved Characterization of Polyoxazolidinones by Incorporating Solubilizing Side Chains

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Facile construction of functional poly(monothiocarbonate) copolymers under mild operating conditions

Abstract: The installation of both oxazolidone and thiocarbonate linkages within a single polymer backbone remains elusive by simple procedures under mild conditions. In this work, we report the construction of copolymers...

Cited by 12 publications

References 33 publications

Catalyst-Free Approach for the Degradation of Bio- and CO2-Sourced Polycarbonates: A Step toward a Circular Plastic Economy

Catalyst-Free Approach for the Degradation of Bio- and CO2-Sourced Polycarbonates: A Step toward a Circular Plastic Economy

Improved Characterization of Polyoxazolidinones by Incorporating Solubilizing Side Chains

Improved Characterization of Polyoxazolidinones by Incorporating Solubilizing Side Chains

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Product

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Catalyst-Free Approach for the Degradation of Bio- and CO₂-Sourced Polycarbonates: A Step toward a Circular Plastic Economy

Catalyst-Free Approach for the Degradation of Bio- and CO₂-Sourced Polycarbonates: A Step toward a Circular Plastic Economy