Moghe Keerti, Sutar A K, Kang I K, Gupta K C
Polymer Research Laboratory, Department of Chemistry, Indian Institute of Technology Roorkee Roorkee 247 667 India
Department of Polymer Science and Engineering, Kyungpook National University 80, Daehak-ro, Buk-gu Daegu 702-701 South Korea
RSC Adv. 2019 Sep 30;9(53):30823-30834. doi: 10.1039/c9ra05811g. eCollection 2019 Sep 26.
Poly(vinylbenzyl chloride--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 ( ) as confirmed by scanning electron microscopy (SEM) and a gas adsorption (BET) method. The prepared polyHIPE monoliths were anchored with -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 h) and low energy of activation (22.4 kJ mol) in the epoxidation of cyclohexene in the presence of hydrogen peroxide (HO) 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.
使用含有固定量的乙烯基苄基氯(VBC,6.0 g,0.0393 mol)和二乙烯基苯(DVB 4.0 g,0.0308 mol)作为油相以及不同体积比的氯化钙水溶液作为内相的高内相乳液(HIPE),制备了具有不同孔隙率的基于聚(乙烯基苄基氯 - 二乙烯基苯)的聚HIPE整体柱。使用Span - 80(2.0 g(4.67 mmol))稳定的HIPE,以过硫酸钾(0.4 g,1.48 mmol)作为引发剂在60℃下进行聚合。通过扫描电子显微镜(SEM)和气体吸附(BET)方法证实,当氯化钙水溶液的体积比从80%变化到90%时,制备的聚HIPE整体柱在其表面形态、比表面积(SA)和孔体积方面显示出显著变化。将制备的聚HIPE整体柱用β - 羟基萘甲醛丙二胺席夫碱配体(HNPn)锚定,然后负载铜(II)离子(HNPn - Cu)以用作催化剂。通过记录其傅里叶变换红外光谱(FT - IR)和紫外可见光谱获得未负载的HNPn - Cu配合物的结构信息。通过原子吸收光谱分析确定负载在HNPn配体锚定的聚HIPE整体柱上的铜(II)离子的量。与未负载的HNPn - Cu催化剂相比,聚HIPE整体柱负载的HNPn - Cu催化剂在40℃下以过氧化氢(HO)作为氧化剂存在时,在环己烯环氧化反应中显示出高催化活性(66.8%)、对环氧环己烷(ECH)的产物选择性(94.8%)、高周转数(0.028 mol mol h)和低活化能(22.4 kJ mol)。聚HIPE负载的HNPn - Cu催化剂还显示出高重复使用性。研究表明,开发具有各种性质以用于特定应用的聚HIPE整体柱有足够的空间。