TY - JOUR
T1 - Carboxylate Salts as Ideal Initiators for the Metal-Free Copolymerization of CO 2 with Epoxides
T2 - Synthesis of Well-Defined Polycarbonates Diols and Polyols
AU - Patil, Naganath G.
AU - Boopathi, Senthil K.
AU - Alagi, Prakash
AU - Hadjichristidis, Nikos
AU - Gnanou, Yves
AU - Feng, Xiaoshuang
N1 - Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/3/26
Y1 - 2019/3/26
N2 - Tetrabutylammonium carbonate (TBAC) which is obtained by treating CO 2 with tetrabutylammonium hydroxide is shown to perform as an ideal difunctional initiator for the copolymerization of carbon dioxide (CO 2 ) and propylene oxide (PO) in the presence of triethylborane (TEB). In this system, CO 2 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 1 H 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.
AB - Tetrabutylammonium carbonate (TBAC) which is obtained by treating CO 2 with tetrabutylammonium hydroxide is shown to perform as an ideal difunctional initiator for the copolymerization of carbon dioxide (CO 2 ) and propylene oxide (PO) in the presence of triethylborane (TEB). In this system, CO 2 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 1 H 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.
UR - http://www.scopus.com/inward/record.url?scp=85063158449&partnerID=8YFLogxK
U2 - 10.1021/acs.macromol.9b00122
DO - 10.1021/acs.macromol.9b00122
M3 - Article
AN - SCOPUS:85063158449
SN - 0024-9297
VL - 52
SP - 2431
EP - 2438
JO - Macromolecules
JF - Macromolecules
IS - 6
ER -