Macroporous thermoset monoliths from glycidyl methacrylate (GMA)-based high internal phase emulsions (HIPEs): Effect of cellulose nanocrystals (CNCs) as filler - Functionalization and removal of Cr(III) from aqueous solutions

Year 2021, , 358 - 368, 31.12.2021

Burcu Kekevi , Ali Eşlek , Emine Hilal Mert

https://doi.org/10.35208/ert.973855

Abstract

Macroporous foams having 80 vol % of nominal porosity were synthesized by the copolymerization crosslinking of glycidyl methacrylate (GMA) based high internal phase emulsions (HIPEs). To alter the mechanical and thermal properties, cellulose nanocrystals (CNCs) were used as filler. For this purpose, CNCs were added to the continuous oil phase during emulsification process at a loading rate of 1, 5 or 7 wt %. Consequently, composite foams were obtained by purification of the polymerized HIPEs (polyHIPEs). The effect of CNCs on the morphological and mechanical properties was investigated. It was found that CNCs have a significant influence on the thermal stability and the compressive strength of the obtained foams. In the end, the neat polyHIPE foam and the polyHIPE/CNC composite foam with 1 wt % of CNC were post-functionalized by reacting phenylimidazole (PIAL) with the epoxy ring of the GMA units. Resulting amine functional foams and the neat foam were utilized in Cr(III) removal from aqueous solutions. It was demonstrated that amine functional foams have a great potential as sorbent materials. The results also showed that the existence of CNCs decreased the performance for removing Cr(III) ions. Nevertheless, functionalization by PIAL significantly improved the selectivity of Cr(III) in comperasion with the neat polyHIPE foam.

Keywords

Amine functionalization, chrome (III) removal, CNC, GMA, macroporous foam

References

• H. Bartl and W. Bonnin, “Über die polymerisation in umgekehrter emulsion,” Die Makromolekulare Chemie, Vol.57, pp.74-95, 1962.
• K.M.L. Taylor-Pashow and J.G. Pribyl, “PolyHIPEs for Separations and Chemical Transformations: A Review,” Solvent Extraction and Ion Exchange, Vol. 37, pp. 1–26, 2019.
• N.R. Cameron and D.C. Sherrington, “High internal phase emulsions (HIPEs) — Structure, prop-erties and use in polymer preparation”. In: Biopolymers Liquid Crystalline Polymers Phase, Emulsion. Advances in Polymer Science, 126, Springer, Berlin, Heidelberg (1996).
• W. Ostwald, “Beiträge zur kenntnis der emulsionen,” Colloid and Polymer Science, Vol. 6, pp.103–109, 1910.
• K.J. Lissant, “The geometry of high-internal-phase-ratio emulsions,” Journal of Colloid and Interface Science, Vol. 22, pp. 462–468, 1966.
• H.H. Mert, M.S. Mert and E.H. Mert, “A statistical approach for tailoring the morphological and mechanical properties of polystyrene PolyHIPEs: looking through experimental design,” Materials Research Express, Vol. 6, 115306, 2019.
• S.D. Kimmins and N.R. Cameron, “Functional Porous Polymers by Emulsion Templating: Recent Advances,”Advanced Functional Materials, Vol. 21, pp. 211–225, 2011.
• S. Yang, L. Zeng, Z. Li, X. Zhang, H. Liu, C. Nie and H. Liu, “Facile approach to glycidyl methacrylate-based polyHIPE monoliths with high epoxy-group content,” European Polymer Journal, Vol. 57, 127–136, 2014.
• N. Brun, S. Ungureanu, H. Deleuze and R. Backov, “Hybrid foams, colloids and beyond: From design to applications”, Chemical Society Reviews, Vol.40, pp.771-788, 2011.
• M. S. Silverstein, “Emulsion-templated porous polymers: A retrospective perspective”, Polymer, Vol. 55, pp. 304–320, 2014.
• J. M. Williams, A. J. Gray, M. H. Wilkerson, “Emulsion stability and rigid foams from styrene or divinylbenzene water-in-oil emulsions”, Langmuir, Vol. 6, pp. 437–444, 1990.
• R. Butler, I. Hopkinson and A. I. Cooper, “Synthesis of Porous Emulsion-Templated Polymers Using High Internal Phase CO2-in-Water Emulsions”, Journal of American Chemical Society, Vol.125, pp. 14473–14481, 2003. C.H. Yao, L. Qi, H.Y. Jia, P.Y. Xin, G.L. Yang, and Y. Chen.” A novel glycidyl methacrylate-based monolith with sub-micron skeletons and well-defined macropores”. Journal of Material Chemistry, Vol. 19, pp. 767–772, 2009.
• P.M. Solozhenkin and A.I. Zouboulis, “Removal of arsenic compounds by chemisorption filtration”, Journal of Mining Science, Vol.43, pp. 212-220, 2007.
• S. De and A. Khan, “Efficient synthesis of multifunctional polymers via thiol–epoxy “click” chemistry”, Chemical Communications, Vol. 48, pp. 3130-3132, 2012.
• A. Br¨andle, A. Khan, Thiol–epoxy ‘click’ polymerization: efficient construction of reactive and functional polymers”, Polymer Chemistry, Vol. 3, pp. 3224-3227, 2012.
• I. Gadwal and A. Khan, “Protecting-group-free synthesis of chain-end multifunctional polymers by combining ATRP with thiol–epoxy ‘click’ chemistry”, Polymer Chemistry, Vol. 4, pp. 2440-2444, 2013.
• H. Gao, M. Elsabahy, E. V. Giger, D. Li, R. E. Prud’homme, J.-C. Leroux, “Aminated Linear and Star-Shape Poly(glycerol methacrylate)s: Synthesis and Self-Assembling Properties”, Biomacromolecules, Vol. 11, pp. 889–895, 2010.
• F. J. Xu, M. Y. Chai, W. B. Li, Y. Ping, G. P. Tang, W. T. Yang, J. Ma and F. S. Liu, “Well-Defined Poly(2-hydroxyl-3-(2-hydroxyethylamino)propyl methacrylate) Vectors with Low Toxicity and High Gene Transfection Efficiency”, Biomacromolecules, Vol.11, pp. 1437–1442, 2010.
• P. Krajnc, N. Leber, D. Štefanec, S. Kontrec, A. Podgornik, “Preparation and characterisation of poly(high internal phase emulsion) methacrylate monoliths and their application as separation media”, Journal of Chromatography A, Vol. 1065, pp.69–73, 2005.
• D. Pahnovik, J. Majer, E. Zagar, S. Kovacic, “Synthesis of hydrogel polyHIPEs from functionalized glycidyl methacrylate”, Polymer Chemistry, Vol. 7, pp. 5132-5138, 2016.
• E. H. Mert, M. A., Kaya, H. Yıldırım, “Preparation and characterization of polyester–glycidyl methacrylate polyHIPE monoliths to use in heavy metal removal: Functional polyHIPE monoliths as metal sorbent”, Designed Monomers and Polymers, Vol. 15, pp. 113-126, 2012.
• E. H. Mert and H. Yıldırım, “Porous functional poly(unsaturated polyester-co-glycidyl methacrylate-co-divinylbenzene) polyHIPE beads through w/o/w multiple emulsions: preparation, characterization and application”, E-Polymers, Vol. 14 (1), pp. 65-73, 2014.
• S. Yang, L. Zeng, Y. Wang, X. Sun, P. Sun, H. Liu, C. Nie, H. Liu, “Facile approach to glycidyl methacrylate-based polyHIPE monoliths with high epoxy-group content”, Colloid and Polymer Science, Vol. 292, 2563–2570, 2014.
• S. Yang, Y. Wang, Y. Jia, X. Sun, P. Sun, Y. Qin, R. Li, H. Liu, C. Nie, “Tailoring the morphology and epoxy group content of glycidylmethacrylate-based polyHIPE monoliths via radiation-inducedpolymerization at room temperature”, Colloid and Polymer Science, Vol. 296, pp. 1005–1016, 2018.
• L. Jin, Q. Sun, Q. Xu, and Y. Xu, “Adsorptive removal of anionic dyes from aqueous solutions using microgel based on nanocellulose and polyvinylamine”, Bioresource Technology, Vol. 197, pp. 348-355, 2015.
• H. Qiao, Y. Zhou, F. Yu, E. Wang, Y. Min, Q. Huang, L. Pang and T. Ma, “Effective removal of cationic dyes using carboxylate-functionalized cellulose nanocrystals”, Chemosphere, Vol. 141, pp. 297-303, 2015.
• A.Barbetta and N.R. Cameron, “Morphology and surface area of emulsion-derived (polyHIPE) solid foams prepared with oil-phase soluble porogenic solvents: span 80 as surfactant”, Macromolecules, Vol. 37, pp. 3188–3201, 2004.
• A. Menner and A. Bismarck, “New evidence for the mechanism of the pore formation in polymerising high internal phase emulsions or why polyHIPEs have an interconnected pore network structure,” Macromolecular Symposia, Vol. 242, pp. 19–24, 2006.
• R.J. Carnachan, M. Bokhari, S.A. Przyborskibc and N.R. Cameron, “Tailoring the morphology of emulsion-templated porous polymers,” Soft Matter, Vol. 2, pp. 608–616, 2006.
• H.H. Mert, M.R. Moghbeli, S. Sajad and E.H. Mert, “Functionalized cellulose nanocrytals (fCNCs) reinforced PolyHIPEs:Tailoring morphological, mechanical and thermal properties,” Reactive and Functional Polymers, Vol. 151, 104572, 2020.
• E. Lizundia, J.L.Vilas and L.M. León, “Crystallization, structural relaxation and thermal degradation in Poly (L-lactide)/cellulose nanocrystal renewable nanocomposites,” Carbohydrate Polymers, Vol. 123, pp. 256-265, 2015.
• F.J. Kilzer and A. Broido, “Speculations on the nature of cellulose pyrolysis,” Pyrodynamics, Vol. 2, pp. 151-163, 1965.
• S. Maiti, J. Jayaramudu, K. Das, S.M. Reddy, R. Sadiku, S.S. Ray and D. Liu, “Preparation and characterization of nano-cellulose with new shape from different precursor,” Carbohydrate Polymers, Vol. 98(1), pp. 562-567, 2013.
• R. Elangovan, L. Philip and K. Chandraraj, “Biosorption of chromium species by aquatic weeds: Kinetics and mechanism studies,” Journal of Hazardous Materials, Vol. 152, pp. 100–112, 2008.