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Metal-Free Alternating Copolymerization of CO2 with Epoxides: Fulfilling "Green" Synthesis and Activity.
J Am Chem Soc. 2016 09 07; 138(35):11117-20.JA

Abstract

Polycarbonates were successfully synthesized for the first time through the anionic copolymerization of epoxides with CO2, under metal-free conditions. Using an approach based on the activation of epoxides by Lewis acids and of CO2 by appropriate cations, well-defined alternating copolymers made of CO2 and propylene oxide (PO) or cyclohexene oxide (CHO) were indeed obtained. Triethyl borane was the Lewis acid chosen to activate the epoxides, and onium halides or onium alkoxides involving either ammonium, phosphonium, or phosphazenium cations were selected to initiate the copolymerization. In the case of PO, the carbonate content of the poly(propylene carbonate) formed was in the range of 92-99% and turnover numbers (TON) were close to 500; in the case of CHO perfectly alternating poly(cyclohexene carbonate) were obtained and TON values were close to 4000. The advantages of such a copolymerization system are manifold: (i) no need for multistep catalyst/ligand synthesis as in previous works; (ii) no transition metal involved in the copolymer synthesis and therefore no coloration of the samples isolated; and (iii) no necessity for postsynthesis purification.

Authors+Show Affiliations

Physical Sciences and Engineering Division and ‡KAUST Catalysis Center, King Abdullah University of Science and Technology (KAUST) , Thuwal 23955, Saudi Arabia.Physical Sciences and Engineering Division and ‡KAUST Catalysis Center, King Abdullah University of Science and Technology (KAUST) , Thuwal 23955, Saudi Arabia.Physical Sciences and Engineering Division and ‡KAUST Catalysis Center, King Abdullah University of Science and Technology (KAUST) , Thuwal 23955, Saudi Arabia.Physical Sciences and Engineering Division and ‡KAUST Catalysis Center, King Abdullah University of Science and Technology (KAUST) , Thuwal 23955, Saudi Arabia.Physical Sciences and Engineering Division and ‡KAUST Catalysis Center, King Abdullah University of Science and Technology (KAUST) , Thuwal 23955, Saudi Arabia.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

27529725

Citation

Zhang, Dongyue, et al. "Metal-Free Alternating Copolymerization of CO2 With Epoxides: Fulfilling "Green" Synthesis and Activity." Journal of the American Chemical Society, vol. 138, no. 35, 2016, pp. 11117-20.
Zhang D, Boopathi SK, Hadjichristidis N, et al. Metal-Free Alternating Copolymerization of CO2 with Epoxides: Fulfilling "Green" Synthesis and Activity. J Am Chem Soc. 2016;138(35):11117-20.
Zhang, D., Boopathi, S. K., Hadjichristidis, N., Gnanou, Y., & Feng, X. (2016). Metal-Free Alternating Copolymerization of CO2 with Epoxides: Fulfilling "Green" Synthesis and Activity. Journal of the American Chemical Society, 138(35), 11117-20. https://doi.org/10.1021/jacs.6b06679
Zhang D, et al. Metal-Free Alternating Copolymerization of CO2 With Epoxides: Fulfilling "Green" Synthesis and Activity. J Am Chem Soc. 2016 09 7;138(35):11117-20. PubMed PMID: 27529725.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Metal-Free Alternating Copolymerization of CO2 with Epoxides: Fulfilling "Green" Synthesis and Activity. AU - Zhang,Dongyue, AU - Boopathi,Senthil K, AU - Hadjichristidis,Nikos, AU - Gnanou,Yves, AU - Feng,Xiaoshuang, Y1 - 2016/08/26/ PY - 2016/8/17/entrez PY - 2016/8/17/pubmed PY - 2016/8/17/medline SP - 11117 EP - 20 JF - Journal of the American Chemical Society JO - J. Am. Chem. Soc. VL - 138 IS - 35 N2 - Polycarbonates were successfully synthesized for the first time through the anionic copolymerization of epoxides with CO2, under metal-free conditions. Using an approach based on the activation of epoxides by Lewis acids and of CO2 by appropriate cations, well-defined alternating copolymers made of CO2 and propylene oxide (PO) or cyclohexene oxide (CHO) were indeed obtained. Triethyl borane was the Lewis acid chosen to activate the epoxides, and onium halides or onium alkoxides involving either ammonium, phosphonium, or phosphazenium cations were selected to initiate the copolymerization. In the case of PO, the carbonate content of the poly(propylene carbonate) formed was in the range of 92-99% and turnover numbers (TON) were close to 500; in the case of CHO perfectly alternating poly(cyclohexene carbonate) were obtained and TON values were close to 4000. The advantages of such a copolymerization system are manifold: (i) no need for multistep catalyst/ligand synthesis as in previous works; (ii) no transition metal involved in the copolymer synthesis and therefore no coloration of the samples isolated; and (iii) no necessity for postsynthesis purification. SN - 1520-5126 UR - https://www.unboundmedicine.com/medline/citation/27529725/Metal_Free_Alternating_Copolymerization_of_CO2_with_Epoxides:_Fulfilling_"Green"_Synthesis_and_Activity_ L2 - https://dx.doi.org/10.1021/jacs.6b06679 DB - PRIME DP - Unbound Medicine ER -
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