title: 1-Butanol absorption in poly(styrene-divinylbenzene) ion exchange resins for catalysis.
abstract: The swelling behaviour of poly(styrene-co-divinylbenzene), P(S-DVB), ion exchange resins in 1-butanol (BuOH) has been studied by means of atomistic classical molecular dynamics simulations (MD). The topological characteristics reported for the resin in the dry state, which exhibited complex internal loops (macropores), were considered for the starting models used to examine the swelling induced by BuOH contents ranging from 10% to 50% w/w. Experimental measurements using a laser diffraction particle size analyzer indicate that swelling causes a volume variation with respect to the dry resin of 21%. According to MD simulations, such a volume increment corresponds to a BuOH absorption of 31-32% w/w, which is in excellent agreement with the indirect experimental estimation (i.e. 31% w/w). Simulations reveal that, independently of the content of BuOH, the density of the swelled resin is higher than that of the dry resin, evidencing that the alcohol provokes important structural changes in the polymeric matrix. Thus, BuOH molecules cause a collapse of the resin macropores when the content of alcohol is ≤20% w/w. In contrast, when the concentration of BuOH is close to the experimental value (∼30% w/w), P(S-DVB) chains remain separated by pores faciliting the access of the reactants to the reaction centers. On the other hand, evaluation of both bonding and non-bonding interactions indicates that the mixing energy is the most important contribution to the absorption of BuOH into the P(S-DVB) resin. Overall, the results displayed in this work represent a starting point for the theoretical study of the catalytic conversion of BuOH into di-n-butyl ether in P(S-DVB) ion exchange resins using sophisticated electronic methods.
authors.affiliation: Departament d'Enginyeria Química, Facultad de Química, Universitat de Barcelona, Martí i Franqués 1, Barcelona E-08028, Spain. perez.macia@ub.edu dcurco@ub.edu.
authors.forename: M A
authors.initials: MA
authors.lastname: Pérez-Maciá
authors.affiliation: Departament d'Enginyeria Química, Facultad de Química, Universitat de Barcelona, Martí i Franqués 1, Barcelona E-08028, Spain. perez.macia@ub.edu dcurco@ub.edu.
authors.forename: D
authors.initials: D
authors.lastname: Curcó
authors.affiliation: Departament d'Enginyeria Química, Facultad de Química, Universitat de Barcelona, Martí i Franqués 1, Barcelona E-08028, Spain. perez.macia@ub.edu dcurco@ub.edu.
authors.forename: R
authors.initials: R
authors.lastname: Bringué
authors.affiliation: Departament d'Enginyeria Química, Facultad de Química, Universitat de Barcelona, Martí i Franqués 1, Barcelona E-08028, Spain. perez.macia@ub.edu dcurco@ub.edu.
authors.forename: M
authors.initials: M
authors.lastname: Iborra
authors.affiliation: Eduard-Zintl-Institut für Anorganische und Physikalische Chemie and Center of Smart Interfaces, Technische Universität Darmstadt, Alarich-Weiss-Straße 10, 64287, Darmstadt, Germany.
authors.forename: F
authors.initials: F
authors.lastname: Rodríguez-Ropero
authors.affiliation: Eduard-Zintl-Institut für Anorganische und Physikalische Chemie and Center of Smart Interfaces, Technische Universität Darmstadt, Alarich-Weiss-Straße 10, 64287, Darmstadt, Germany.
authors.forename: N F A
authors.initials: NF
authors.lastname: van der Vegt
authors.affiliation: Departament d'Enginyeria Química, E.T.S. d'Enginyers Industrials de Barcelona, Universitat Politécnica de Catalunya, Diagonal 647, Barcelona E-08028, Spain. carlos.aleman@upc.edu and Center for Research in Nano-Engineering, Universitat Politécnica de Catalunya, Campus Sud, Edifici C', C/Pascual I Vila s/n, Barcelona E-08028, Spain.
authors.forename: Carlos
authors.initials: C
authors.lastname: Aleman
mesh_terms: D020001:1-Butanol / Q000737:chemistry*; D002384:Catalysis; D007475:Ion Exchange Resins / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D011137:Polystyrenes / Q000737:chemistry*
chemical_list: D007475:Ion Exchange Resins; D011137:Polystyrenes; C432006:divinylbenzene-polystyrene copolymer; D020001:1-Butanol