ß-Cyclodextrin-derived diallylamine salt: Synthesis and its copolymerizations.

ABSTRACT

A diallyl amine salt monomer bearing a ß-CD substituent was cyclopolymerized for the first time. The reaction of 6-O-toluenesulfonyl-ß-cyclodextrin [(C6H10O5)6-(C5H7)]-CH2OTs with diallylamine followed by protonation afforded the diallylamine salt monomer [(C6H10O5)6-(C5H7)]-CH2NH+(CH2CH=CH2)2 Cl-] (I). The cyclopolymerization of monomer I and its copolymerization with monomer [Me2N+(CH2CH=CH2)2 Cl-] (II), [-O2CCH2NH+(CH2CH=CH2)2] (III), [H2O3PCH2NH+(CH2CH=CH2)2 Cl-] (IV) or [HO2CCH2CH(CO2H)NH+(CH2CH=CH2)2 Cl-] (V) yielded a series of copolymers having residues of ß-CD and glycine or methyl phosphonate or aspartic acid. Terpolymerization in the presence of SO2 afforded polymers with alternating placements of the SO2 units. The solution properties of the pH-responsive polyzwitterions, including their viscosity, were examined. The water-insoluble terpolymer I/V/SO2 with 20 mol% ß-CD residues removed the organic micropollutant 2-naphthol from an aqueous system via host/guest complexation. This work paves the way for the possible synthesis of cross-linked polymers that can simultaneously remove organic micropollutants and toxic metal ions (by complexation with the chelating glycine, aspartic acid, and aminomethyl phosphonate ligands) from contaminated aqueous systems.