A Joined Theoretical−Experimental Investigation on the ¹H and ¹³C NMR Signatures of Defects in Poly(vinyl chloride)

Abstract

1H and 13C chemical shifts of PVC chains have been evaluated using quantum chemistry methods in order to evidence and interpret the NMR signatures of chains bearing unsaturated and branched defects. The geometrical structures of the stable conformers have been determined using molecular mechanics and the OPLS force field and then density functional theory with the B3LYP functional and the 6-311G(d) basis set. The nuclear shielding tensor has been calculated at the coupled-perturbed Kohn-Sham level (B3LYP exchange-correlation functional) using the 6-311+G(2d,p) basis set. The computational scheme accounts for the large number of stable conformers of the PVC chains, and average chemical shifts are evaluated using the Maxwell-Boltzmann distribution. Moreover, the chemical shifts are corrected for the inherent and rather systematic errors of the method of calculation by employing linear regression equations, which have been deduced from comparing experimental and theoretical results on small alkane model compounds containing Cl atoms and/or unsaturations. For each type of defect, PVC segments presenting different tacticities have been considered because it is known from linear PVC chains that the racemic (meso) dyads are characterized by larger (smaller) chemical shifts. NMR signatures of unsaturations in PVC chains have been highlighted for the internal -CH=CH- and -CH=CCl- units as well as for terminal unsaturations like the chloroallylic -CH=CH-CH2Cl group. In particular, the 13C chemical shifts of the two sp2 C atoms are very close for the chloroallylic end group. The CH2 and CHCl units surrounding an unsaturation present also specific 13C chemical shifts, which allow distinguishing them from the others. In the case of the proton, the CH2 unit of the -CHCl-CH2-CCl=CH- segment presents a larger chemical shift (2.6-2.7 ppm), while some CHCl units close to the -CH=CH- unsaturations appear at rather small chemical shifts (3.7 ppm). The -CH2Cl and -CHCl-CH2Cl branches also display specific signatures, which result in large part from modifications of the equilibrium conformations and their reduced number owing to the increased steric interactions. These branches lead to the appearance of 13C peaks at lower field associated either to the CH unit linking the -CH2Cl and -CHCl-CH2Cl branches (50 ppm) or to the CHCl unit of the ethyl branches (60 ppm). The corresponding protons resonate also at specific frequencies: 3.5-4.0 ppm for the -CH2Cl branch or 3.8-4.2 ppm for the terminal unit of the -CHCl-CH2Cl branch. Several of these signatures have been detected in the experimental 1H and 13C NMR spectra and are consistent with the reaction mechanisms.

Non‐Oxidative Conversion of 1,2‐Dichloroethane in a Non‐Thermal Plasma and Characterisation of the Polymer Formed

“…[32] Termination by radical combination and disproportionation is explained in Figure 6a and b, respectively. Another termination mechanism, which results in terminal unsaturation in the polymer backbone chain, as described by d'Antuono et al [35] , is also possible in this case, as evidenced of this is also seen in the polymer characterisation.…”

“…[36] The presence of double bonds in the polymer is indicated by the peaks in 5.6-5.9 ppm. [35,36] 3.7.4. 13 C NMR The 13 C NMR of the polymer is shown in Figure 8.…”

“…The peaks in the region of 44.5-48 ppm are attributed to the CH 2 group which is a part of the main chain repeating group. [35,36] The peaks in the region of 55-62 ppm are assigned to CHCl main chain repeating group [35,36] . The peaks in the region of 106-108 ppm can be assigned to a CH group which is a part of a double bond in the oligomer.…”

Reaction of carbon tetrachloride with methane in a non-equilibrium plasma at atmospheric pressure, and characterisation of the polymer thus formed

“…4. M a n u s c r i p t [33]. The broad peak from 120 to 140 ppm may be indicative of more than one M a n u s c r i p t 15 species including aromatic structures.…”

“…The broad peak from 120 to 140 ppm may be indicative of more than one M a n u s c r i p t 15 species including aromatic structures. Species such as -CHCl-CH=CH 2 are likely to have a signature in this region [33].…”