Abstract
Quaternization reaction of poly(vinylbenzyl chloride) with hexamine was monitored using NMR at different time intervals and temperatures in this study. The amine to polymer ratios of 0.2:1, 0.33:1, and 1:1 were employed, and the progress of the reaction was monitored instantly after the addition of reactants. NMR was recorded at the intervals of every 10 min until for about an hour. Temperature was also varied from 30 to 60 °C, and progress of the reaction was monitored by NMR. The quaternization reaction was complete immediately after the addition of the reactants at 60 °C, whereas at low temperatures, the reaction proceeded at much lower rates. Even at low temperatures, the reaction proceeded at a faster rate when the amine content was higher. The quaternization reaction rate with different hexamine (HMA)-to-poly(vinylbenzyl chloride) (PVBC) ratios follows the order 1:1 > 0.33:1 > 0.2:1.
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References
Varcoe JR, Slade RCT (2004) Prospects for alkaline anion-exchange membranes in low temperature fuel cells. Fuel Cells 5:187–200
Sata T, Teshima K, Yamaguchi T (1996) Permselectivity between two anions in anion exchange membranes crosslinked with various diamines in electrodialysis. J Polym Sci, Part A: Polym Chem 34(8):1475–1482
Leng Y, Chen G, Mendoza AJ, Tighe TB, Hickner MA, Wang CY (2012) Solid-state water electrolysis with an alkaline membrane. J Am Chem Soc 134:9054–9057
Hibbs MR, Fujimoto CH, Cornelius CJ (2009) Synthesis and characterization of poly(phenylene)-based anion exchange membranes for alkaline fuel cells. Macromolecules 42(21):8316–8321
Zhao Z, Wang J, Li S, Zhang S (2011) Synthesis of multi-block poly (arylene ether sulfone) copolymer membrane with pendant quaternary ammonium groups for alkaline fuel cell. J Power Sources 196(10):4445–4450
Fang J, Shen PK (2006) Quaternized poly (phthalazinon ether sulfone ketone) membrane for anion exchange membrane fuel cells. J Membr Sci 285(1-2):317–322
Li L, Wang Y (2005) Quaternized polyethersulfone Cardo anion exchange membranes for direct methanol alkaline fuel cells. J Membr Sci 262(1-2):1–4
Lu W, Shao ZG, Zhang G, Li Y, Zhao Y, Yi B (2013) Preparation of anion exchange membranes by an efficient chloromethylation method and homogeneous quaternization/crosslinking strategy. Solid State Ionics 245–246:8–18
Komkova EN, Stamatialis DF, Strathmann H, Wessling M (2004) Anion-exchange membrane containing diamines: preparation and stability in alkaline solution. J Membr Sci 244(1-2):25–34
Pandey AK, Goswami A, Sen D, Mazumder S, Childs RF (2003) Formation and characterization of highly crosslinked anion-exchange membranes. J Membr Sci 217(1- 2):117–130
Jacobs WA, Heidelberger M (1915) The quaternary salts of hexamethylenetetramine: I Substituted benzyl halides and the hexamethylenetetraminium salts derived therefrom. J Biol Chem 20:659–683
Luo Y, Guo J, Wang C, Chu D (2012) Fuel cell durability enhancement by cross-linking alkaline anion exchange membrane electrolyte. Electrochem Commun 16:65–68
Robertson NJ, Kostalik HA, Clark TJ, Mutolo PF, Abruna HD, Coates GW (2010) Tunable high performance cross-linked alkaline anion exchange membranes for fuel cell applications. J Am Chem Soc 132:3400–3404
Pan J, Li Y, Zhuang L, Lu J (2010) Self-crosslinked alkaline polymer electrolyte exceptionally stable at 90 °C. Chem Commun 46:8597–8599
Qiao J, Fu J, Liu L, Liu Y, Sheng J (2012) Highly stable hydroxyl anion conducting membranes poly(vinyl alcohol)/poly(acrylamide-co-diallyldimethylammonium chloride) (PVA/PAADDA) for alkaline fuel cells: Effect of cross-linking. Int J Hydrogen Energy 37:4580–4589
Merle G, Hosseiny SS, Wessling M, Nijmeijer K (2012) New cross-linked PVA based polymer electrolyt membranes for alkaline fuel cells. J Membr Sci 409-410:191–199
Sahoo SK, Liu W, Samuelson LA, Kumar J, Cholli AL (2002) Biocatalytic polymerization of p-Cresol: An in-situ NMR approach to understand the coupling mechanism. Macromolecules 35:9990–9998
Preusser C, Hutchinson RA (2013) An in-Situ NMR study of radical copolymerization kinetics of acrylamide and non-ionized acrylic acid in aqueous solution. Macromol Symp 333:122–137
Mahdavian AR, Abdollahi M, Bijanzadeh HR (2004) Kinetic study of radical polymerization. III: solution polymerization of acrylamide by 1H-NMR. J Appl Poly Sci 93:2007–2013
Cutie SS, Smith PB, Henton DE, Staples TL, Powell C (1997) Acrylic acid polymerization kinetics. J Polym Sci, Part B: Polym Phys 35:2029–2047
Cutie SS, Hento DE, Powell C, Reim RE, Smith PB, Staples TL (1997) The effects of MEHQ on the polymerization of acrylic acid in the preparation of superabsorbent gels. J Appl Polym Sci 64:577–589
Cao YC, Wang X, Mamlouk M, Scott K (2011) Preparation of alkaline anion exchange polymer membrane from methylated melamine grafted poly (vinylbenzyl chloride) and its fuel cell performance. J Mater Chem 21:12910–12916
Varcoe JR, Slade RCT, Yee ELH (2006) An alkaline polymer electrochemical interface: a breakthrough in application of alkaline anion-exchange membrane in fuel cells. Chem Commun 13:1428–1429
Rivera A, Bernal JS, Motta JR, Dusek M, Palatinus L (2011) Synthesis and structural studies of a new class of quaternary ammonium salts, which are derivatives of cage adamanzane type aminal 1, 3, 6, 8-tetraazatricyclo[4.3.1.13,8]undecane (TATU). Chem Cent J 5:55
Katzfub A, Gogel V, Jorissen L, Kerres J (2013) The application of covalently cross- linked BrPPO as AEM in alkaline DMFC. J Membr Sci 425–426:131–140
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The corresponding author gratefully acknowledges CSIR-CECRI for providing financial assistance through the in-house project (project code: OLP 0075).
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Vengatesan, S., Vasudevan, D. & Radhakrishnan, S. Time- and temperature-resolved in-situ NMR studies on simultaneous quaternization/cross-linking of poly(vinylbenzyl chloride) polymer with hexamine. Colloid Polym Sci 293, 3439–3448 (2015). https://doi.org/10.1007/s00396-015-3712-7
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DOI: https://doi.org/10.1007/s00396-015-3712-7