Controlling the tacticity in the polymerization of n-isopropylacrylamide: a computational study

Özaltın, Furuncuoğlu T. and Değirmenci, İsa and Aviyente, Viktorya and Atılgan, Canan and De Sterck, B. and Van Speybroeck, V. and Waroquier, M. (2011) Controlling the tacticity in the polymerization of n-isopropylacrylamide: a computational study. Polymer, 52 (24). pp. 5503-5512. ISSN 0032-3861

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In this study, the effect of alcohols as solvents on the kinetics and the tacticity of poly(NIsopropylacrylamide)(PNIPAM) is investigated with a combined static and molecular dynamics set of computational tools. Classical molecular dynamics calculations have been carried out to determine the location of the solvent molecules in the proximity of the monomer and the dimer. A combined implicit/explicit solvent model was used for the evaluation of the kinetics of the dimeric polymer chains. Rate constants are calculated with the B3LYP/6-311 G(d,p)//B3LYP/6-31 G(d), BMK/6-311 G(d,p)//B3LYP/6-31 G(d), and MPWB1K/6-311 G(d,p)//B3LYP/6-31 G(d) methodologies via the standard transition state theory. We show that due to the proximity of the eNH and carbonyl groups on the syndiotactic propagating dimeric and trimeric chains, the alcohol can stabilize the corresponding transition states by forming a bridge between these functionalities and accelerate this path more than its isotactic counterpart. In agreement with experiment, the increase in the syndiotactic PNIPAM and the acceleration of the reaction in the presence of t-BuOH is predicted with all the DFT functionals utilized in this study.
Item Type: Article
Uncontrolled Keywords: NIPAM; Modeling; Tacticity
Subjects: Q Science > QD Chemistry > QD450-801 Physical and theoretical chemistry
Divisions: Faculty of Engineering and Natural Sciences > Academic programs > Materials Science & Eng.
Faculty of Engineering and Natural Sciences
Depositing User: Canan Atılgan
Date Deposited: 03 Jan 2012 11:21
Last Modified: 30 Jul 2019 15:06

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