Spectroscopic studies of poly(vinyl chloride) and its deuterated derivatives

Poly(vinyl chloride) (PVC) and all its deuterated derivatives were prepared by variation of the polymerization method and polymerization temperature to study the structure of PVC and the mechanism of addition polymerization by infrared spectroscopy and high resolution NMR spectroscopy. The CH and CH 2 stretching modes of PVC were assigned completely from the infrared spectra of PVC‐α d 1 , PVC‐β,β d 2 and PVC‐ d 3 . The frequencies of the CCI stretching modes of the polymers depended not only on the substituents in the trans position to the Cl atom across both adjacent CC bonds, but also on the atom attached to the C atom of the CCl bond. The frequency shifts were used to assign the CCl stretching modes of PVC‐β d 1 and PVC‐α,β d 2 and to study the opening of the double bond of VC in the addition polymerization. The differences of the chemical shifts of the α and β protons of PVC due to the tacticity were determined experimentally by PVC‐β,β d 2 and PVC‐α d 1 without using the spin‐decoupling technique. With PVC‐α,β d 2 , the conception of the tetrad was required to interpret the four observed peaks whose intensities changed with the polymerization temperature and the trans–cis composition of the monomer used.