Since cyclopolymerization mechanism of diallyl quaternary ammonium salts in aqueous media was introduced by Butler and coworkers, diallylamine polymers have received considerable attention for possible industrial applications ranging from the use in water treatment to papermaking, textiles, pharmaceuticals, coatings and adhesives. Most of their attempt to polymerize diallylamine derivatives have been carried out in aqueous solution with inorganic acid. In this paper, we report the synthesis of a series of N-aryl substituted diallylamine and polymerization of them in neat conditions. We also have synthesized model compounds having five and six member rings and investigated the cyclic structure of poly(N,N-diallylamino-2-pyrimidine) based on the NMR spectra. Diallylamine monomers bearing phenyl, 2-pyridinyl, 4-pyidinyl, 2-pyrimidinyl, and benzyl group were prepared by Buchwald-Hartwig coupling reaction or other suitable synthetic procedures. The bulk polymerization of a series of N-substituted diallylamine monomers were carried out using AIBN at 70 degree C. While the aromatic ring directly substituted diallylamine monomers exhibited the ability of polymerization, N-benzyldiallylamine didn’t polymerize substantially under this reaction condition. All the polymers are soluble to many organic solvents but insoluble to neutral water. Although the cyclic diallylamine polymer structure was initially believed to be a six membered ring from the thermodynamic stand point, the most of the cases except the monomer possessing substituents at β-carbon have been found to be a five-membered ring because of the kinetic preference. To confirm the structure of the obtained polymers, the model compounds having a five and a six-membered ring were synthesized. Compared with 1H-NMR spectra of these model compounds, we conclude that poly(N,N-diallylamino-2-pyrimidine) has exclusively five member ring cyclic structure with cis and trans configuration.

Cyclopolymerization of N-aryl substituted diallylamines

256th National Meeting (2018)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.