Activated carbonates: Enabling the synthesis of differentiated polymers via solution carbonation

Kamps, Jan Henk; Groote, Ramon; Baus, Mathilde; Vermeulen, Han; Hoeks, Theo; Heijden, Ruud van der; Sijbesma, Rint P.; Heuts, Johan P. A.

doi:10.1016/j.eurpolymj.2020.109901

Cited by 9 publications

(10 citation statements)

References 29 publications

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“…The notable methods for preparation of aromatic polycarbonates include: the Schotten‐Baumann reaction of bisphenol and phosgene in an amine‐catalyzed interfacial polycondensation reaction, [46] direct reaction of bisphenol with phosgene in a solvent in the presence of a tertiary amine, [47] solution polycondensation of bisphenol with bis(methyl salicyl) carbonate [48] at a temperature of 120 °C and high temperature polycondensation ofbisphenol with either diphenyl or dimethyl carbonate [49] . The finishing stage in polycarbonate synthesis by melt polycondensation route is carried out in the temperature range 250–320 °C under reduced pressure [50] .…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Characterization and UV‐Crosslinking of Aromatic (Co)polycarbonates Bearing Pendant Azido Groups

et al. 2022

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A new series of (co)polycarbonates bearing pendent azido groups was synthesized by polycondensation of varying molar proportions of 4, 4'-(5-azidopentane-2, 2-diyl) diphenol and bisphenol-A with triphosgene. The chemical structures, compositions and random nature of (co)polycarbonates were confirmed by NMR spectroscopy. Inherent viscosities and numberaverage molecular weights of (co)polycarbonates were in the range 0.63-0.77 dL g À 1 and 35,400-43,400 g mol À 1 , respectively indicating the formation of reasonably high molecular weight polymers. (Co)polycarbonates could be cast into tough, transparent and flexible films from chloroform solutions. (Co)polycarbonates were further characterized using IR spectroscopy, XRD, TGA and DSC. The thermal crosslinking of (co)polycarbonates bearing pendant azido groups was studied by DSC analysis. Independently, (co)polycarbonates bearing pendant azido groups were exposed to UV irradiation at wavelength of 254 nm and decomposition reaction of azido groups was monitored by FT-IR spectroscopy. The complete decomposition of azido groups was observed with exposure time of 30 min. The formed cross-linked (co)polycarbonates exhibited improved % char yield values compared to parent (co)polycarbonates. The measurement of mechanical properties of representative crosslinked (co)polycarbonates indicated increase in tensile strength and Young's modulus and decrease in % elongation compared to corresponding parent linear (co)polycarbonates.

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Section: Resultsmentioning

confidence: 99%

Synthesis, Characterization and UV‐Crosslinking of Aromatic (Co)polycarbonates Bearing Pendant Azido Groups

et al. 2022

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“…The significantly faster rate at 120 °C as compared to 60 °C is expected and explains the difference in molar masses obtained at these two temperatures after 1 h of reaction as reported in our previous publication. [ 5 ] Assuming a negligible contribution from the reverse reaction on the initial rates and any chain length dependence of the kinetics, the bimolecular rate coefficients, k , for the forward reaction in Scheme 1 and as defined in Equation (), were estimated from the data shown in Figure 1

\begin{matrix} true \\ right - \frac{d false[OH false]}{d t} = k [OH] [ϕ] \end{matrix}

…”

Section: Resultsmentioning

confidence: 99%

“…[ 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. In that study, however, we did not focus on any kinetic aspects and, except for one polymerization at 60 °C, all the reported polymerizations were carried out at 120 °C.…”

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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“…The residual HCl in the product sometimes causes serious problems that prevent applications of the chemicals and polymers produced from COCl 2 . Thus, exploration of alternative compounds has been an important research subject in organic chemistry. − Bis(trichloromethyl)carbonate (BTC), generally called triphosgene, has been preferably used as the phosgene substitute in laboratory-scale syntheses . BTC, which is a solid under standard conditions, allows direct substitution reactions and/or in situ generation of COCl 2 in the solution through reactions with nucleophiles .…”

Section: Introductionmentioning

confidence: 99%

“…In this background, diphenyl carbonate [(PhO) 2 CO] is utilized as a phosgene substitute that allows nucleophilic substitution reactions with alcohols and amines (Scheme ). , The reactions eliminate phenol to give the corresponding carbonate esters, carbamates, and urea derivatives. Less attention has been paid to alkyl carbonates, except for dimethyl carbonate (DMC), which are cheaper than aryl carbonates, but have generally lower reactivity .…”

Section: Introductionmentioning

confidence: 99%

Reactivity and Product Selectivity of Fluoroalkyl Carbonates in Substitution Reactions with Primary Alcohols and Amines

et al. 2022

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The present study reports a systematic investigation of the substitution reactions of a series of symmetric and unsymmetric fluoroalkyl carbonates with primary alcohols or amines. The reactivity of the haloalkyl carbonate depends mainly on the electrophilicity and steric crowdedness of the carbonyl group and the leaving ability of the haloalkyl alcohols. Diethyl carbonate as a reference substrate showed no reaction with the alcohol or amine. However, bis(2,2,2-trifluoroethyl) carbonate [(F3-EtO)2CO] having electron-withdrawing trifluoroethyl groups enabled substitution reactions, with relatively higher reactivities to those for diphenyl carbonate [(PhO)2CO]. Furthermore, (F6-iPrO)2CO, bearing two sets of hexafluoroisopropyl groups, showed dramatic acceleration of the reactions, in which the observed reactivities were similar to those for bis(perfluorophenyl) carbonate [(F5-PhO)2CO]. The electrophilicity of the carbonyl group and the leaving ability of the alcohols in the series of haloalkyl carbonates were found to be correlated with the wavenumbers of their carbonyl groups in IR spectra and pK a for the eliminated alcohols, respectively. Since the eliminated fluoroalkyl alcohols exhibit weak affinity with the organic products and have lower boiling points owing to a characteristic property of the fluoroalkyl group, they could be readily removed from the product by simple evaporation below 100 °C with or without reduced pressure.

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Activated carbonates: Enabling the synthesis of differentiated polymers via solution carbonation

Cited by 9 publications

References 29 publications

Synthesis, Characterization and UV‐Crosslinking of Aromatic (Co)polycarbonates Bearing Pendant Azido Groups

Synthesis, Characterization and UV‐Crosslinking of Aromatic (Co)polycarbonates Bearing Pendant Azido Groups

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

Reactivity and Product Selectivity of Fluoroalkyl Carbonates in Substitution Reactions with Primary Alcohols and Amines

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