Synthesis of Polycarbonates and Poly(ether carbonate)s Directly from Carbon Dioxide and Diols Promoted by a Cs2CO3/CH2Cl2 System

Bian, Shi; Pagan, Cale; Artemyeva, Anastasia A.; Du, Guodong

doi:10.1021/acsomega.6b00278

Cited by 30 publications

(23 citation statements)

References 68 publications

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“…The T g s of the polyphosphonate homopolymers prepared from more rigid diols ( CHDM‐S/CHDM‐Se and BDM‐S/BDM‐Se ) are higher than those of the polyphosphonate homopolymers prepared from the more flexible diol ( tetraEG‐S/tetraEG‐Se ) as may be expected. Typically, polyesters and polycarbonates derived from 1,4‐benzenedimethanol and 1,4‐cyclohexanedimethanol show very similar T g s and T m s, with the former polymers often having higher values 31–33 . However, in the polyphosphonates, the CHDM polymers possess higher T g s than do the BDM polymers by up to 18°C.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and characterization of modular polyphosphonate homopolymers and copolymers

Totsch

Stanford

Klep

et al. 2020

Journal of Polymer Science

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Linear polyphosphonates with the generic formula –[P(Ph)(X)OR′O]n– (X = S or Se) have been synthesized by polycondensations of P(Ph)(NEt2)2 and a diol (HOR′OH = 1,4‐cyclohexanedimethanol, 1,4‐benzenedimethanol, tetraethylene glycol, or 1,12‐dodecanediol) followed by reaction with a chalcogen. Random copolymers have been synthesized by polycondensations of P(Ph)(NEt2)2 and mixture of two of the diols in a 2:1:1 mol ratio followed by reaction with a chalcogen. Block copolymers with the generic formula –[P(Ph)(X)OR′O](x + 2) –[P(Ph)(X)OR′O](x + 3)– (X = S or Se) have been synthesized by the polycondensations of Et2N[P(Ph)(X)OR′O](x + 2)P(Ph)NEt2 oligomers with HOR′O[P(Ph)(X)OR′O](x + 3)H oligomers followed by reaction with a chalcogen. The Et2N[P(Ph)(X)OR′O](x + 2)P(Ph)NEt2 oligomers are prepared by the reaction of an excess of P(Ph)(NEt2)2 with a diol while the HOR′O[P(Ph)(X)OR′O](x + 3)H oligomers are prepared by the reaction of P(Ph)(NEt2)2 with an excess of the diol. In each case the excess, x is the same and determines the average block sizes. All of the polymers were characterized using 1H, 13C{1H}, and 31P{1H} NMR spectroscopy, TGA, DSC, and SEC. 31P{1H} NMR spectroscopy demonstrates that the random and block copolymers have the expected arrangements of monomers and, in the case of block copolymers, verifies the block sizes. All polymers are thermally stable up to ~300°C, and the arrangements of monomers in the copolymers (block vs. random) affect their degradation temperatures and Tg profiles. The polymers have weight average MWs of up to 3.8 × 104 Da.

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Section: Resultsmentioning

confidence: 99%

Synthesis and characterization of modular polyphosphonate homopolymers and copolymers

Totsch

Stanford

Klep

et al. 2020

Journal of Polymer Science

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“…In a similar concept, Du and coworkers proposed a straightforward methodology to copolymerize various diols with CO 2 using Cs 2 CO 3 as the base (4 eq) and dichloromethane as the co-reagent (6.2 eq) in NMP [131]. Interestingly, the nature of the diol dictates the microstructural features of the polymer backbone toward either a polycarbonate or a poly(ether carbonate), which alternates carbonates and ether linkages.…”

Section: Direct Copolymerization Via Alkylationmentioning

confidence: 99%

En Route to CO2-Based (a)Cyclic Carbonates and Polycarbonates from Alcohols Substrates by Direct and Indirect Approaches

et al. 2022

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This review is dedicated to the state-of-the art routes used for the synthesis of CO2-based (a)cyclic carbonates and polycarbonates from alcohol substrates, with an emphasis on their respective main advantages and limitations. The first section reviews the synthesis of organic carbonates such as dialkyl carbonates or cyclic carbonates from the carbonation of alcohols. Many different synthetic strategies have been reported (dehydrative condensation, the alkylation route, the “leaving group” strategy, the carbodiimide route, the protected alcohols route, etc.) with various substrates (mono-alcohols, diols, allyl alcohols, halohydrins, propargylic alcohols, etc.). The second section reviews the formation of polycarbonates via the direct copolymerization of CO2 with diols, as well as the ring-opening polymerization route. Finally, polycondensation processes involving CO2-based dimethyl and diphenyl carbonates with aliphatic and aromatic diols are described.

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“…However, synthesizing polymer or polymer platforms from biomass-based materials by directly introducing CO 2 is rare. Although some biomass-derived oxiranes or aliphatic alcohols (diols) will be compatible with the conversion reaction or direct copolymerization of CO 2 [21,22], furan-based biomass-derived monomers, such as 5-(hydroxymethyl)furfural (HMF) and 2,5-bis(hydroxymethyl)furan (BHMF) have not been utilized in CO 2 immobilization.…”

Section: Introductionmentioning

confidence: 99%

Self-Healable and Recyclable Biomass-Derived Polyurethane Networks through Carbon Dioxide Immobilization

et al. 2021

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Due to growing environmental issues, research on carbon dioxide (CO2) use is widely conducted and efforts are being made to produce useful materials from biomass-derived resources. However, polymer materials developed by a combined strategy (i.e., both CO2-immobilized and biomass-derived) are rare. In this study, we synthesized biomass-derived poly(carbonate-co-urethane) (PCU) networks using CO2-immobilized furan carbonate diols (FCDs) via an ecofriendly method. The synthesis of FCDs was performed by directly introducing CO2 into a biomass-derived 2,5-bis(hydroxymethyl)furan. Using mechanochemical synthesis (ball-milling), the PCU networks were effortlessly prepared from FCDs, erythritol, and diisocyanate, which were then hot-pressed into films. The thermal and thermomechanical properties of the PCU networks were thoroughly characterized by thermogravimetric analysis, differential scanning calorimetry, dynamic (thermal) mechanical analysis, and using a rheometer. The self-healing and recyclable properties of the PCU films were successfully demonstrated using dynamic covalent bonds. Interestingly, transcarbamoylation (urethane exchange) occurred preferentially as opposed to transcarbonation (carbonate exchange). We believe our approach presents an efficient means for producing sustainable polyurethane copolymers using biomass-derived and CO2-immobilized diols.

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Synthesis of Polycarbonates and Poly(ether carbonate)s Directly from Carbon Dioxide and Diols Promoted by a Cs₂CO₃/CH₂Cl₂ System

Cited by 30 publications

References 68 publications

Synthesis and characterization of modular polyphosphonate homopolymers and copolymers

Synthesis and characterization of modular polyphosphonate homopolymers and copolymers

En Route to CO2-Based (a)Cyclic Carbonates and Polycarbonates from Alcohols Substrates by Direct and Indirect Approaches

Self-Healable and Recyclable Biomass-Derived Polyurethane Networks through Carbon Dioxide Immobilization

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