Cd(ii) and Zn(ii) coordination polymer-assisted CO2/cyclohexene oxide copolymerization with a double metal cyanide catalyst

It is attractive but challenging to develop a cocatalyst for CO2/cyclohexene oxide (CHO) copolymerization with a double metal cyanide (DMC) catalyst. In this study, we synthesized three coordination polymers (CPs) [Cd(3N3PY)(NDC)]·0.58H2O (1), [Zn(3N3PY)(IPA)]·3H2O (2) and [Cd(3N3PY)(NPA)]·2DMF·2H2O...

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Bibliographic Details
Published in:CrystEngComm 2024-03, Vol.26 (12), p.1701-1709
Main Authors: Zi-Qing Huang, Jia-Qi, Chen, Xiao-Yu, Zhang, Cheng-Kai, Yuan, Wang, Peng, Zhao, Yue, Bao-Cheng, Zhao, Wei-Xin, Qi, Wei-Yin, Sun
Format: Article
Language:English
Subjects:
Carbon dioxide
Catalysts
Chemical synthesis
Coordination polymers
Copolymerization
Cyclohexene
Dicarboxylic acids
Hydrogen bonding
Naphthalene
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Summary:It is attractive but challenging to develop a cocatalyst for CO2/cyclohexene oxide (CHO) copolymerization with a double metal cyanide (DMC) catalyst. In this study, we synthesized three coordination polymers (CPs) [Cd(3N3PY)(NDC)]·0.58H2O (1), [Zn(3N3PY)(IPA)]·3H2O (2) and [Cd(3N3PY)(NPA)]·2DMF·2H2O (3) (3N3PY = 4′-(4-(1H-1,2,4-triazol-1-yl)phenyl)-2,2′:6′,2′′-terpyridine, H2NDC = 2,6-naphthalene dicarboxylic acid, H2IPA = isophthalic acid, H2NPA = 2,2′-dinitro-4,4′-biphenyldicarboxylic acid). Crystal structural analyses show that 1–3 are different one-dimensional (1D) chains that further assemble into three-dimensional (3D) supramolecular structures by π–π and hydrogen bonding interactions. CPs 1–3 were applied as cocatalysts to assist DMC for CO2/CHO copolymerization and the efficient proportion of carbonate P–OC(O)O– in the product is 59% achieved for 2 at 80 °C in 1 MPa CO2. The proportion of carbonate F(CO2) and conversion rate of CHO (CCHO) are 63% and 93%, respectively. The mechanistic study on structure–activity relationship and chemoselectivity was performed.
ISSN:1466-8033
DOI:10.1039/d3ce01289a