Issue 21, 2014

One-pot controllable synthesis of oligo(carbonate-ether) triol using a Zn-Co-DMC catalyst: the special role of trimesic acid as an initiation-transfer agent

Abstract

A one-pot synthesis of oligo(carbonate-ether) triol was realized by the copolymerization of CO2 and propylene oxide (PO) using a zinc-cobalt double metal cyanide (Zn-Co-DMC) catalyst in the presence of 1,3,5-benzenetricarboxylic (trimesic) acid (TMA). The catalytic activity ranged from 0.3 to 1.0 kg gāˆ’1 DMC under various copolymerization conditions. The structure of the oligo(carbonate-ether) triol was clearly confirmed, providing sound evidence for the special role played by the TMA, i.e., that it acted as an initiation-transfer agent. In the first stage the TMA initiated PO homo-polymerization to afford oligo-ether triol via a core-first approach in the presence of Zn-Co-DMC. After all of the TMA was consumed, the in situ formed oligo-ether triol acted as new chain transfer agent to participate in the copolymerization, forming carbonate-ether segments and therefore the oligo(carbonate-ether) triol. Since every molecule of TMA participated in initiation and propagation steps, the molecular weight of the triol depended on the amount of TMA used rather than the amount of Zn-Co-DMC. Consequently, the number average molecular weight (Mn) of the oligo(carbonate-ether) triol could be well controlled from 1400 to 3800 g molāˆ’1 with a relatively narrow polydispersity index (PDI) (1.15ā€“1.45), and its carbonate unit content (CU) could be adjusted between 20% and 54%.

Graphical abstract: One-pot controllable synthesis of oligo(carbonate-ether) triol using a Zn-Co-DMC catalyst: the special role of trimesic acid as an initiation-transfer agent

Supplementary files

Article information

Article type
Paper
Submitted
25 Apr 2014
Accepted
27 Jun 2014
First published
30 Jun 2014

Polym. Chem., 2014,5, 6171-6179

Author version available

One-pot controllable synthesis of oligo(carbonate-ether) triol using a Zn-Co-DMC catalyst: the special role of trimesic acid as an initiation-transfer agent

S. Liu, Y. Qin, X. Chen, X. Wang and F. Wang, Polym. Chem., 2014, 5, 6171 DOI: 10.1039/C4PY00578C

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