Abstract
We describe the synthesis of polycarbonate by means of the polycondensation of diol formate and dialkyl carbonate through an ester-carbonate exchange reaction. The reaction of dodecane-1,12-diol formate (1a) and dipropyl carbonate (2e) in the presence of 5 mol%, compared to 1a, potassium tert-butoxide (tBuOK) in diglyme at 120 °C under reduced pressure (90–100 Torr) afforded high-molar-mass polycarbonate (PC). When polycondensation of 1a and diethyl carbonate (2d) was conducted in the presence of poly(1,12-dodecamethylene isophthalate) (PEs) in toluene at 60 °C under reduced pressure, both the synthesis of PC and the exchange reaction between the PC and PEs backbones proceeded simultaneously, and a statistical copolymer of PC and PEs was obtained. The composition of PC and PEs in the copolymer could be arbitrarily altered by changing the feed ratio of the monomers to PEs. The crystallization temperature (Tc) of the copolymer increased linearly with increasing PC content in the copolymer from −10.8 °C (100% PEs) to 47.3 °C (100% PC).
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Brunelle DJ Polycarbonates. In: Mark HF, editor. Encyclopedia of polymer science and technology, 4th Edition, vol. 10. Hoboken: John Wiley & Sons, Inc.; 2014. p. 354–85.
Diepens M, Gijsman P. Photodegradation of bisphenol a polycarbonate. Polym Degrad Stab. 2007;92:397–406.
Levchik SV, Weil ED. Overview of recent developments in the flame retardancy of polycarbonates. Polym Int. 2005;54:981–98.
Yu W, Maynard E, Chiaradia V, Arno MC, Dove AP. Aliphatic polycarbonates from cyclic carbonate monomers and their application as biomaterials. Chem Rev. 2021;121:10865–907.
Artham T, Doble M. Biodegradation of aliphatic and aromatic polycarbonates. Macromol Biosci. 2008;8:14–24.
Feng J, Zhuo R-X, Zhang X-Z. Construction of functional aliphatic polycarbonates for biomedical applications. Prog Polym Sci. 2012;37:211–36.
Brunelle DJ, Shannon TG. Preparation and polymerization of bisphenol a cyclic oligomeric carbonates. Macromolecules 1991;24:3035–44.
Brunelle DJ, Boden EP, Shannon TG. Remarkably selective formation of macrocyclic aromatic carbonates: Versatile new intermediates for the synthesis of aromatic polycarbonates. J Am Chem Soc. 1990;112:2399–402.
Brunelle DJ, Shannon TG. Preparation of functionalized polycarbonates via ring-opening polymerization of diverse mixed oligomeric cyclic carbonates. Makromol Chem Macromol Symp. 1991;42-43:155–66.
Brunelle DJ, Krabbenhoft HO, Bonauto DK. Preparation of crystalline and solvent-resistant polycarbonates via ring-opening polymerization of cyclic oligomers. Macromol Symp. 1994;77:117–24.
Hodge P. Entropically driven ring-opening polymerization of strainless organic macrocycles. Chem Rev. 2014;114:2278–312.
Brunelle DJ. Advances in polycarbonates: An overview. Advances in polycarbonates. 898. Washington, D. C.: American Chemical Society; 2005. p. 1–5.
Kricheldorf HR, Böhme S, Schwarz G, Schultz C-L. Cyclic polycarbonates by polycondensation of bisphenol a with triphosgene. Macromolecules 2004;37:1742–8.
Haba O, Itakura I, Ueda M, Kuze S. Synthesis of polycarbonate from dimethyl carbonate and bisphenol-a through a non-phosgene process. J Polym Sci, Part A: Polym Chem. 1999;37:2087–93.
Zhu W, Huang X, Li C, Xiao Y, Zhang D, Guan G. High-molecular-weight aliphatic polycarbonates by melt polycondensation of dimethyl carbonate and aliphatic diols: Synthesis and characterization. Polym Int. 2011;60:1060–7.
Sweileh BA, Al-Hiari YM, Kailani MH, Mohammad HA. Synthesis and characterization of polycarbonates by melt phase interchange reactions of alkylene and arylene diacetates with alkylene and arylene diphenyl dicarbonates. Molecules 2010;15:3661–82.
Wang Z, Yang X, Liu S, Hu J, Zhang H, Wang G. One-pot synthesis of high-molecular-weight aliphatic polycarbonates via melt transesterification of diphenyl carbonate and diols using Zn(OAc)2 as a catalyst. RSC Adv. 2015;5:87311–9.
Katoh T, Ogawa Y, Ohta Y, Yokozawa T. Synthesis of polyester by means of polycondensation of diol ester and dicarboxylic acid ester through ester–ester exchange reaction. J Polym Sci. 2021;59:787–97.
Ganguly A, Channe P, Jha R, Mitra S, Saha S. Review on transesterification in polycarbonate–poly(butylene terephthalate) blend. Polym Eng Sci. 2021;61:650–61.
Montaudo G, Puglisi C, Samperi F. Copolymer composition: A key to the mechanisms of exchange in reactive polymer blending. In: Fakirov S, editor. Transreactions in condensation polymers. Weinheim: Wiley-VCH; 1999. p. 159–93.
Porter RS, Jonza JM, Kimura M, Desper CR, George ER. Polyesters ii: A review of phase behavior in binary blends: Amorphous, crystalline, liquid crystalline, and on transreaction. Polym Eng Sci. 1989;29:55–62.
Liu Y, Ranucci E, Söderqvist Lindblad M, Albertsson A-C. New biodegradable polymers from renewable sources: Polyester-carbonates based on 1,3-propylene-co-1,4-cyclohexanedimethylene succinate. J Polym Sci, Part A: Polym Chem. 2001;39:2508–19.
Liang J, Ye S, Wang S, Xiao M, Meng Y. Design and structure of catalysts: Syntheses of carbon dioxide-based copolymers with cyclic anhydrides and/or cyclic esters. Polym J. 2021;53:3–27.
Acknowledgements
This work was supported by JST-Mirai Program Grant Number JPMJMI18A2, Japan.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare no competing interests.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Rights and permissions
About this article
Cite this article
Katoh, T., Saso, M., Ohta, Y. et al. Synthesis of polycarbonates and polycarbonate/polyester copolymers through an ester-carbonate exchange reaction. Polym J 54, 1063–1069 (2022). https://doi.org/10.1038/s41428-022-00663-7
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41428-022-00663-7