Effect of the Substituent Position on the Anionic
Copolymerization of Styrene Derivatives: Experimental Results and
Density Functional Theory Calculations
Version 3 2019-06-25, 15:08
Version 2 2019-06-12, 19:38
Version 1 2019-06-12, 19:35
Posted on 2019-06-25 - 15:08
In a combined synthetic, kinetic
and theoretical study, the living
anionic copolymerization of styrene and its ring-methylated derivatives ortho-, meta-, and para-methylstyrene (MS) was examined by real-time 1H NMR spectroscopy
in the nonpolar solvents toluene-d8 and
cyclohexane-d12 as well as by density
functional theory calculations. Based on the NMR kinetics data, reactivity
ratios for each comonomer pair were determined by the Kelen–Tüdős
method and numerical integration of the copolymerization equation
(Contour software). The reaction pathway was modeled and followed
by density functional theory (DFT) calculations to validate and predict
the experimentally derived reactivity ratios. Unexpectedly, two of
the three styrene derivatives showed completely different reactivities
in copolymerization, governed by the position of the methyl group.
While para-MS is considerably less reactive than
styrene, resulting in gradient copolymers (rS = 2.62; rpMS = 0.37), ortho-MS showed the opposite behavior
and is more reactive than styrene (rS =
0.44; roMS = 2.47), leading
to a reversal of the copolymers’ gradient. The substitution
in the meta-position had nearly no influence on monomer reactivity,
and copolymers with close to random comonomer distribution were formed
(rS = 0.81; rmMS = 1.21). In all cases, the theoretical calculations
showed good to excellent agreement with the experimental data. Monomer
reactivities correlate with the chemical shifts of the β-carbon
signals in 13C NMR spectra that are predictive for the
gradient structure. The results demonstrate the possibility of tailoring
and validating the polymer structures of functional polystyrene copolymers
by the choice of the substitution pattern of styrene derivatives,
using both experimental and theoretical approaches.
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Johann, Tobias; Leibig, Daniel; Grune, Eduard; Müller, Axel H.E.; Frey, Holger (2019). Effect of the Substituent Position on the Anionic
Copolymerization of Styrene Derivatives: Experimental Results and
Density Functional Theory Calculations. ACS Publications. Collection. https://doi.org/10.1021/acs.macromol.9b00747
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AUTHORS (5)
TJ
Tobias Johann
DL
Daniel Leibig
EG
Eduard Grune
AM
Axel H.E. Müller
HF
Holger Frey