Poly(vinylbenzyl chloride- co-divinyl benzene) polyHIPE monolith-supported o-hydroxynaphthaldehyde propylenediamine Schiff base ligand complex of copper(ii) ions as a catalyst for the epoxidation of cyclohexene

Keerti Moghe; A K Sutar; I K Kang; K C Gupta

doi:10.1039/c9ra05811g

Poly(vinylbenzyl chloride- co-divinyl benzene) polyHIPE monolith-supported o-hydroxynaphthaldehyde propylenediamine Schiff base ligand complex of copper(ii) ions as a catalyst for the epoxidation of cyclohexene

RSC Adv. 2019 Sep 30;9(53):30823-30834. doi: 10.1039/c9ra05811g. eCollection 2019 Sep 26.

Authors

Keerti Moghe¹, A K Sutar¹, I K Kang², K C Gupta^{1

2}

Affiliations

¹ Polymer Research Laboratory, Department of Chemistry, Indian Institute of Technology Roorkee Roorkee 247 667 India kcgptfcy@iitr.ac.in keertik@hormail.com +91 1332 273560 +91 132 285325.
² Department of Polymer Science and Engineering, Kyungpook National University 80, Daehak-ro, Buk-gu Daegu 702-701 South Korea ikkang@knu.ac.kr +82 53 950 6623 +82 53 950 5629.

Abstract

Poly(vinylbenzyl chloride-co-divinyl benzene)-based polyHIPE monoliths of different porosities were prepared using high-internal-phase emulsions (HIPEs) containing a fixed amount of vinylbenzyl chloride (VBC, 6.0 g, 0.0393 mol) and divinyl benzene (DVB 4.0 g, 0.0308 mol) as the oil phase and different volume ratios of aqueous calcium chloride as the internal phase. Span-80 (2.0 g (4.67 mmol))-stabilized HIPEs were polymerized at 60 °C using potassium persulfate (0.4 g, 1.48 mmol) as the initiator. Upon varying the volume ratio of aqueous calcium chloride from 80 to 90%, the prepared polyHIPE monoliths have shown significant variations in their surface morphology, specific surface area (SA), and pore volumes (V _p) as confirmed by scanning electron microscopy (SEM) and a gas adsorption (BET) method. The prepared polyHIPE monoliths were anchored with o-hydroxynaphthaldehyde propylenediamine Schiff base ligand (HNPn) and then loaded with copper(ii) ions (HNPn-Cu) to act as a catalyst. The structural information of unsupported HNPn-Cu complexes was obtained by recording its FT-IR and UV-visible spectra. The amount of copper(ii) ions loaded onto HNPn ligand-anchored polyHIPE monoliths was determined by atomic absorption spectroscopic analysis. In comparison to unsupported HNPn-Cu catalyst, the polyHIPE monolith-supported HNPn-Cu catalyst has shown high catalytic activity (66.8%), product selectivity for epoxycyclohexane (ECH) (94.8%), high turn over number (0.028 mol mol^-1 h^-1) and low energy of activation (22.4 kJ mol^-1) in the epoxidation of cyclohexene in the presence of hydrogen peroxide (H₂O₂) as an oxidant at 40 °C. The polyHIPE-supported HNPn-Cu catalyst also shows high reuse applications. Studies show that there is sufficient scope to develop polyHIPE monoliths with various properties for specific applications.