Synthesis and physicochemical properties of dual-responsive acrylic acid/butyl acrylate cross-linked nanogel systems

J Colloid Interface Sci. 2019 Nov 15:556:313-323. doi: 10.1016/j.jcis.2019.08.066. Epub 2019 Aug 20.

Abstract

Hypothesis: A cross-linked amphiphilic nanogel containing a high mole% of hydrophilic pH-responsive moiety can provide enhanced functionality regarding stimuli-responsiveness, water-dispersibility, hydrophobic substance loading, and structural stability under harsh environmental conditions. These nanogels could be synthesized using a one-pot procedure for large-scale applications. Moreover, the interplay of various interaction forces in these colloidal systems is being investigated.

Experiments: Model nanogels consisting of acrylic acid-butyl acrylate-ethylene glycoldimethacrylate were synthesized using an emulsion copolymerization via a seeded semi-batch process under an acidic condition. The structures were assessed by Fourier transform infrared spectroscopy and potentiometric-conductometric titrations. Zeta potential, field-emission scanning electron microscopy, and transmission electron microscopy were used to evaluate the dispersion stability, size distribution, and structural distribution, respectively. Their stimuli-responsive behavior was studied by combining static and dynamic light scattering and titration analyses.

Findings: Monodisperse nanospheres of approximately 150 nm were successfully prepared by implementing a one-pot practical pathway. These nanogels displayed a dual thermo- and pH-responsive behavior, reflecting the high efficiency of physical cross-linking make it ideal for drug delivery and oil industry applications. Moreover, a novel symmetric pH-activated morphology transformation behavior was revealed. Accordingly, a compositional distribution was proposed and assessed by exploring the polymerization process.

Keywords: Acrylic acid/butyl acrylate; Dual pH- and thermo-responsive nanogel; Dual physical and chemical cross-linking; Emulsion polymerization; Morphology transformation.