Aspartic acid in a new role: Synthesis and application of a pH-responsive cyclopolymer containing residues of the amino acid

Abstract

The reaction between diallylamine and dimethyl maleate afforded the Michael addition product dimethyl N,N-diallylaspartate [(CH2CH–CH2)2NCH(CO2Me)CH2CO2Me] I, which upon treatment with dry HCl and ester hydrolysis with aqueous HCl gave its hydrochloride salt [(CH2CH–CH2)2NH+CH(CO2Me)CH2CO2Me Cl−] II and N,N-diallylaspartic acid hydrochloride [(CH2CH–CH2)2NH+CH(CO2H)CH2CO2H Cl−] III, respectively. The new monomers II and III underwent cyclopolymerization to give, respectively, cationic polyelectrolytes (CPEs) poly(II) and poly(III). Under the influence of pH, triprotic acid (+) poly(III) was equilibrated to water-insoluble diprotic polyzwitterionic acid (±) IV, water-soluble monoprotic poly(zwitterion–anion) (± −) V, and its conjugate base polydianion (=) VI. The protonation constants of the carboxyl group and trivalent nitrogen in VI have been determined. A 20-ppm concentration of IV is effective in inhibiting the precipitation of CaSO4 from its supersaturated solution with an ≈100% scale inhibition efficiency for a duration of 50h at 40°C. The aqueous two-phase systems (ATPSs) of VI and polyoxyethylene have been studied. The transformation of water-soluble VI to insoluble IV makes it a recycling ATPS as it can be recycled by precipitation at a lower pH.