Activated carbonates: enabling the synthesis of differentiated polycarbonate resins via melt transcarbonation

Kamps, Jan Henk; Hoeks, Theo; Kung, Edward; Lens, J.P.; McCloskey, Patrick J.; Noordover, Bart A. J.; Heuts, Johan P. A.

doi:10.1039/c6py00925e

Cited by 27 publications

(29 citation statements)

References 10 publications

(15 reference statements)

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“…Using an activated carbonate such as bis(methyl salicyl) carbonate (BMSC) instead of DPC has proven to ameliorate this situation in melt polymerization allowing for significantly lower temperatures. [ 2–4 ] Recently, we reported the efficient synthesis of BPA‐based copolycarbonates in solution at relatively low temperatures using BMSC as the carbonate donor. [ 5 ] We demonstrated the incorporation of thermally labile monomers and showed the feasibility of producing multiblock copolycarbonates via this route.…”

Section: Introductionmentioning

confidence: 99%

High Molar Mass Polycarbonate via Dynamic Solution Transcarbonation Using Bis(methyl salicyl) Carbonate, an Activated Carbonate

Aerts

Kroonen

Kamps

et al. 2021

Macro Chemistry & Physics

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High molar mass polycarbonate is synthesized via a solution transcarbonation of bis(methyl salicyl) carbonate and bisphenol‐A at temperatures between 60 and 160 °C without the removal of the condensate, allowing the incorporation of thermosensitive monomers into polycarbonate. Kinetic and equilibrium studies show that the polymerization is 20–30 times faster at 120 °C compared to 60 °C, whereas the equilibrium Mw increases from 11 × 103 g mol−1 at 120 °C to 16 × 103 g mol−1 at 60 °C. This polycondensation is characterized by very high equilibrium constants ranging from 0.8 × 103 at 160 °C to 4.1 × 103 at 60 °C, corresponding to standard enthalpies and entropies of polymerization: −19 kJ mol−1 < ΔH0 < −11 kJ mol−1 and 13 J mol−1 K−1 < ΔS0 < 28 J mol−1 K−1. Without removal of the condensate, the system is shown to be dynamic and completely reversible when changing the temperature. Good predictability of this polycondensation is reported, where only at very low starting monomer concentrations, the formation of cyclics leads to deviations from the predicted behavior.

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Section: Introductionmentioning

confidence: 99%

High Molar Mass Polycarbonate via Dynamic Solution Transcarbonation Using Bis(methyl salicyl) Carbonate, an Activated Carbonate

Aerts

Kroonen

Kamps

et al. 2021

Macro Chemistry & Physics

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“…In this process, DPC is prepared in several steps from carbon dioxide (CO 2 ). Nevertheless, there is a significant disadvantage associated with the utilization of DPC as a monomer: phenol, eliminated along with the polymerization of bisphenol‐A and DPC, can hardly be removed from the reaction system to shift the equilibrium between the monomers and PC, owing to its high boiling point . Therefore, the molecular weight of the obtained polymer is lower than that produced from phosgene.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Fluorinated Dialkyl Carbonates from Carbon Dioxide as a Carbonyl Source

et al. 2020

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Fluorinated dialkyl carbonates (DACs), which serve as environmentally benign phosgene substitutes, were produced successfully from carbon dioxide either directly or indirectly. Nucleophilic addition of 2,2,2‐trifluoroethanol to carbon dioxide and subsequent reaction with 2,2,2‐trifluoroethyltriflate (3 a) afforded bis(2,2,2‐trifluoroethyl) carbonate (1) in up to 79 % yield. Additionally, carbonate 1 was obtained through the stoichiometric reaction of 3 a and cesium carbonate. Although bis(1,1,1,3,3,3‐hexafluoro‐2‐propyl) carbonate (4) was difficult to obtain by either of the above two methods, it could be synthesized through the transesterification of carbonate 1.

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“…It is a solid material with a melting temperature range between 61 and 64°C and is known to be thermally stable up to 270°C, making it suitable for use in melt polycondensation reactions to prepare, e.g., polyesters or polycarbonates. [10][11][12][13][14][15][16] In a previously published study, 17 malonated polyester resins were developed affording strongly improved adhesion performance over especially highly converted…”

Section: Introductionmentioning

confidence: 99%

Michael addition curable coatings from renewable resources with enhanced adhesion performance

Noordover¹,

Liu²,

McCracken³

et al. 2020

J Coat Technol Res

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Novel malonate-functional polyesters from biobased and potentially biobased monomers were developed and cured through the base-catalyzed carbon-Michael addition reaction with acryloyl-functional oligomers. Both drop-in monomers, such as fully biobased diethyl malonate, and alternative raw materials, such as isosorbide and vegetable oil, were introduced. Isosorbide-based polyesters show improved performance to humidity in terms of adhesion on epoxy-amine primer, while vegetable oil-containing resins lead to improved coating appearance due to better flow and levelling. This study demonstrates that biobased malonate resins, having renewable contents up to 53%, offer attractive performance benefits in 2K RMA paints. It is anticipated that, with the development of additional fully biobased polyols, renewable contents in excess of 80% can be achieved.

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Activated carbonates: enabling the synthesis of differentiated polycarbonate resins via melt transcarbonation

Cited by 27 publications

References 10 publications

High Molar Mass Polycarbonate via Dynamic Solution Transcarbonation Using Bis(methyl salicyl) Carbonate, an Activated Carbonate

High Molar Mass Polycarbonate via Dynamic Solution Transcarbonation Using Bis(methyl salicyl) Carbonate, an Activated Carbonate

Synthesis of Fluorinated Dialkyl Carbonates from Carbon Dioxide as a Carbonyl Source

Michael addition curable coatings from renewable resources with enhanced adhesion performance

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