In order to understand the origin of the tacticity splitting in the NMR spectra of poly(lactic acid), monomer and dimer model compounds were synthesized and their 1H and 13C NMR chemical shifts were observed. Two stable conformations were obtained from Ramachandran map calculated as a function of the internal rotation angles for the monomer model using Gaussian 09 calculations. Four preferred conformations were selected and optimized for each dimer model. The conformations of neighboring residues were energetically interdependent. The 1H and 13C chemical shifts for dimer model compounds were calculated by averaging the occurrence probabilities obtained from the optimized conformational energies and the calculated chemical shift of each conformation. It was confirmed that the solvent effect on the tacticity-dependent relative chemical shifts was small from the NMR experiments of the model compound observed in different solvents, dimethyl sulfoxide, chloroform, and chloroform/carbon tetrachloride (20/80 v/v) mixture. Good agreement between observed and calculated chemical shifts was obtained for the relative chemical shifts of isotactic and syndiotactic 1H and 13C NMR peaks of the dimer model compounds. The observed tacticity splitting of poly(lactic acid) at the diad level was rationalized on the basis of these chemical shift calculations.

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The physical properties of poly(lactic acid) (PLA) are influenced by its stereoregularity and stereosequence distribution, and its polymer stereochemistry can be effectively studied by NMR spectroscopy. In previously published NMR studies of PLA tacticity, the NMR data were fitted to pair-addition Bernoullian models. In this work, we prepared several PLA samples with a tin catalyst at different L,L-lactide and D,D-lactide ratios. Upon analysis of the tetrad intensities with the pair-addition Bernoullian model, we found substantial deviations between observed and calculated intensities due to the presence of transesterification and racemization during the polymerization processes. We formulated a two-state (pair-addition Bernoullian and single-addition Bernoullian) model, and it gave a better fit to the observed data. The use of the two-state model provides a quantitative measure of the extent of transesterification and racemization, and potentially yields useful information on the polymerization mechanism.