Novel elastic rubbers from CO2-based polycarbonates

Giulia Chiarioni, Martin van Duin, Paolo P. Pescarmona*

*Corresponding author for this work

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We report the fixation of carbon dioxide (CO2) into novel rubber polymers based on polycarbonate domains. Our strategy consisted in the atom-efficient terpolymerisation of CO2 with a long-alkyl-chain epoxide and an unsaturated epoxide to obtain polycarbonates with a glass transition temperature (Tg) below room temperature and with pendant double bonds along the backbone to enable peroxide-promoted cross-linking, thus generating an elastic rubber. First, a wide range of epoxides with long alkyl chains (C6-C12) were coupled with CO2 to give polycarbonates with high yields, using a binary catalytic system consisting of an aluminium amino-tris(phenolate) complex and bis(triphenylphosphoranylidene)ammonium chloride (PPNCl). The synthesised polycarbonates were characterised using FTIR and NMR spectroscopy to determine yields and selectivity, using DSC to measure the Tg, and using GPC to obtain the molecular weight distribution. Next, the terpolymerisation was carried out by including allyl glycidyl ether (AGE) in the reaction mixture together with a long-alkyl-chain epoxide and CO2. Almost complete epoxide conversions (81-100%) and extremely high selectivity (>97%) towards the desired polycarbonates were achieved, with only traces of the cyclic carbonate side-products. The obtained polycarbonates displayed a Tg < 0 °C and thus behave as low-viscosity fluids at room temperature. The pendant unsaturated groups introduced with the AGE monomers allowed cross-linking of the terpolymers with dicumyl peroxide, leading to an elastic rubber-like behaviour as witnessed by their markedly decreased solubility in gel-content tests and by their storage modulus, loss modulus, and Tg, which were determined by dynamic mechanical analysis (DMA). In summary, we have successfully demonstrated that the terpolymerisation of long-chain epoxides, AGE and CO2 yields polycarbonates that can be cross-linked to obtain elastic rubber properties, thus opening the prospects for a new range of applications for CO2-based green polycarbonates.

Original languageEnglish
Pages (from-to)7612-7626
Number of pages15
JournalGreen Chemistry
Issue number19
Publication statusPublished - 16-Aug-2023

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