The dimerization constant (Kg) of acrylic acid and the association constant of the comonomer complex between acrylic acid and 1‐vinyl‐2‐pyrrolidone (K1) have been determined in chloroform by means of IR and 1H NMR spectroscopy: Kd=(2.0±0.2) × 103litre mol−1 and K1=68.5±0.5 litre mol−1. A detailed equation for the copolymer composition considering the participation of the intermolecular complexes in the chain propagation has been derived with the help of a specific regular three addition states Markov chain. Applying a numerical procedure for fitting the experimental curve for the comonomer composition, this equation has been used in the estimation of the dimer and the comonomer complex relative reactivities. The considerably higher reactivities of the two complexes compared with that of the monomers are accounted for by the π‐electrons' greater delocalization in the transition states involving the complexes species.
The association constant of the H-complex formation between acrylic acid and 1-vinyl-2-pyrrolidone in tetrahydrofuran at 22°C ( K , = 1350moll-') was determined by means of 'H NMR spectroscopy. A detailed equation for the copolymer composition, accounting for the participation in the chain propagation of the above complex and that between acid and solvent molecules, was derived. It was used for evalution of the relative reactivities of the complexes discussed and of the uncomplexed 1 -vinyl-2-pyrrolidone molecules. K e y words: copolymerization, l-vinyl-2-pyrrolidone, acrylic acid, H-complex relative reactivity, solvent effect.
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