Rigid biobased polycarbonates with good processability based on a spirocyclic diol derived from citric acid. Issue 12 (5th June 2020)

• Record Type: Journal Article
• Authors: Bonjour, Olivier; Liblikas, Ilme; Pehk, Tõnis; Khai-Nghi, Truong; Rissanen, Kari; Vares, Lauri; Jannasch, Patric
• Is Part Of: Green chemistry. Volume 22:Issue 12(2020)
• Page Start: 3940
• Page End: 3951
• Publication Date: 2020-06-05
• Subjects: Environmental chemistry -- Industrial applications -- Periodicals; Environmental management -- Periodicals; 660
• DOI: 10.1039/d0gc00849d
• Languages: English
• ISSNs: 1463-9262

Abstract

Abstract : A bicylic diketone is derived from citric acid and readily ketalized with trimethylolpropane to produce a spirodiol monomer for rigid, high-molecular weight, melt processable biobased polycarbonates. Abstract : Introducing biobased polymers from renewable sources for use as high-performance thermoplastics with high demands on mechanical rigidity, transparency, thermal stability, as well as good processability, is a significant challenge. In the present work we have designed and prepared a rigid biobased bis-spirocylic diol by di-cycloketalization of a bicyclic diketone ( cis -bicyclo[3.3.0]octane-3, 7-dione, obtained from citric acid) using trimethylolpropane. This spiro-diol monomer has two reactive primary hydroxyl groups and the synthesis from inexpensive biobased starting materials is straightforward and readily upscalable, involving no chromatographic purification. In order to explore the usefulness of the new monomer, it was employed in melt polycondensations with diphenylcarbonate at up to 280 °C to form rigid fully amorphous polycarbonates (PC s). Molecular weights (MWs) up to M n = 28 kg mol −1 were achieved, and thermal and dynamic mechanical measurements showed glass transitions up to T g = 100 °C, with no thermal decomposition until T d ∼350 °C. Solvent cast films had excellent mechanical flexibility and strength, as well as a high transparency with only slight coloration. Results by dynamic melt rheology implied that the high-MW PC s had a good processability at 170 °C, with a stable shear modulus over time, but started to degrade via chain scission reactions when the temperature approached 200 °C. In conclusion, the present work demonstrates the straightforward preparation of the citric acid-based spiro-diol, and indicates that it is an efficient building block for the preparation of rigid biobased PCs and other condensation polymers.