Determination of the sequence distribution and ionization constant of poly(acrylic acid‐co‐vinylamine) by C‐13 NMR

Abstract

Three copolymers of poly(acrylic acid‐co‐vinylamine) containing 12% (SP12). 30% (SP30), and 52% (SP52) amino groups were synthesized from poly(acrylic acid) by means of the Schmidt reaction. These copolymers were analyzed by C‐13 NMR and the results compared wiih the previously analyzed homopolymers. The various comonomer sequence distributions were identified by means of peak areas. It was determined thai (1) the reactivity was not significantly influenced by the triad taciicity of the parent poly(acrylic acid), (2) the final copolymer is characterized by an essentially alternating sequence, and (3) there is extensive lactam formation between neighboring carboxyl and amino groups. In terms of nearest neighbor effects, the relative rales of amine formation are k1/k0 ≈ 0.3 and k2/k0 ≈ 0. A C‐13 NMR pH titration of SPI2 showed that the carboxyl group with a neighboring amino group is more acidic man a carboxyl group flanked by two carboxyl groups.

N-Benzylated Poly(vinylamine): Synthesis, Characterization, and Catalytic Activity in Ester Cleavage

“…Compound 2 was synthesized from polymerization and acid hydrolysis of JV-vinyl-tert-butylcarbamate (NVTBC) obtained by the method of Hart,13 adapted by Hugues and Saint Pierre.14 The molecular weight of 2 (M" = 36 600) was obtained from viscosimetric measurements in 0.1 M NaCl/0.1 M NaOH using the relation [77] = 6.2 X 10-3Mna88. 15 Synthesis of N-Benzylated Poly(vinylamine) (3). The reaction is described in Figure 1.…”