Phosphorus-containing smart, multifunctional polymers towards materials with dual stimuli responsivity, self-aggregation ability and tunable wettability

Abstract

A simple, inexpensive and recyclable photo-induced reversible deactivation radical polymerization (RDRP) of a phosphorus-containing monomer, dimethyl(methacryloyloxymethyl) phosphonate (MAPC1) in ionic liquid (without the need for any conventional photoinitiators or dye sensitizers) is developed for the first time to produce low dispersity (Đ ≤ 1.24) phosphorus-containing polymer, PMAPC1 (at least up to 20200 g mol−1) and a series of well-defined multifunctional PMAPC1-b-poly(M) diblock copolymers (where “M” represents polyethylene glycol methacrylate (PEGMA), 2,2,3,3,4,4,5,5-octafluoropentylacrylate (OFPA) and 2-hydroxyethyl methacrylate (HEMA)) thereof. Kinetic monitoring of the photoRDRP of MAPC1 demonstrated good control of the polymerization. Temporal control, catalyst and ionic liquid recyclability of the polymerization was also demonstrated. The synthesized PMAPC1-b-PPEGMA diblock copolymers exhibited a dual (pH and temperature) stimuli-responsive behavior. Cloud point of PMAPC1-b-PPEGMA diblock copolymers can be tuned by changing the PEGMA mol% in the BCP. Amphiphilic PMAPC1-b-PHEMA diblock copolymer undergoes self-aggregation forming spherical nanoobjects. Phosphonate ester moieties of the synthesized diblock copolymers were selectively hydrolyzed to promising PMAPC1(OH)2-b-poly(M) diblock copolymers that could be used for many applications, including dual stimuli-responsive materials, materials with tunable hydrophobicity, and self-aggregation ability.