Carboxylate Salts as Ideal Initiators for the Metal-Free Copolymerization of CO2 with Epoxides: Synthesis of Well-Defined Polycarbonates Diols and Polyols
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2020-03-13
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ArticleAuthors
Patil, NaganathaBoopathi, Senthil
Alagi, Prakash
Hadjichristidis, Nikolaos

Gnanou, Yves

Feng, Xiaoshuang
KAUST Department
Chemical Science ProgramKAUST Catalysis Center (KCC)
Physical Sciences and Engineering (PSE) Division
KAUST Grant Number
BAS/1/1374-01-01Date
2019-03-13Online Publication Date
2019-03-13Print Publication Date
2019-03-26Permanent link to this record
http://hdl.handle.net/10754/631782
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Tetrabutylammonium carbonate (TBAC) which is obtained by treating CO2 with tetrabutylammonium hydroxide is shown to perform as an ideal difunctional initiator for the copolymerization of carbon dioxide (CO2) and propylene oxide (PO) in the presence of triethylborane (TEB). In this system, CO2 thus serves as the initiating moiety of its own copolymerization with epoxides when used in the form of a carbonate salt. Based on this remarkable result, mono-, tri-, and tetrafunctional ammonium carboxylate initiators and also other difunctional carboxylate initiators were synthesized and used for the synthesis of well-defined ω-hydroxyl-polycarbonates with linear and star structures. Well-defined telechelics, three- and four-armed star samples of molar mass varying from 1 kg/mol to 10 kg/mol, with around 95% carbonate content, were successfully synthesized. The structure of the obtained polycarbonate ω-polyols were characterized by 1H NMR, MALDI-TOF, and GPC. The terminal hydroxyl functionality of polycarbonate diol was further used for polycondensation with diisocyanates to afford polyurethanes. Finally, taking TBAC as an example, the recyclability of this ammonium-based initiator is demonstrated for the preparation of polycarbonate diols.Citation
Patil NG, Boopathi SK, Alagi P, Hadjichristidis N, Gnanou Y, et al. (2019) Carboxylate Salts as Ideal Initiators for the Metal-Free Copolymerization of CO2 with Epoxides: Synthesis of Well-Defined Polycarbonates Diols and Polyols. Macromolecules 52: 2431–2438. Available: http://dx.doi.org/10.1021/acs.macromol.9b00122.Sponsors
This research work is supported by KAUST under baseline funding (BAS/1/1374-01-01).Publisher
American Chemical Society (ACS)Journal
MacromoleculesAdditional Links
https://pubs.acs.org/doi/10.1021/acs.macromol.9b00122ae974a485f413a2113503eed53cd6c53
10.1021/acs.macromol.9b00122