Light-Mediated Thiol–Ene Polymerization in Miniemulsion: A Fast Route to Semicrystalline Polysulfide Nanoparticles

Abstract

Historically, the synthesis of aqueous polymer dispersions has focused on radical chain-growth polymerization of low-cost acrylate or styrene emulsions. Herein, we demonstrate the potential of UV-initiated thiol–ene step-growth radical polymerization, departing from a nontransparent difunctional monomer miniemulsion based on ethylene glycol dithiol and diallyl adipate. Performed without solvent and at ambient conditions, the photopolymerization process is energy-effective, environmentally friendly, and ultrafast, leading to full monomer consumption in 2 s, upon irradiating a miniemulsion contained in a 1 mm thick quartz cell microreactor. The resultant linear poly(thioether ester) particles have an average diameter of 130 nm. After water evaporation, they yield a clear elastomeric film combining chemical resistance and high degree of crystallinity (55%).

Emerging Corrosion Inhibitors for Interfacial Coating

“…Their synthesis was performed in water, at ambient temperature, and without the use of any organic solvent. The resultant linear poly (thioether ester) particles had an average diameter of 130 nm [68]. In another recent work, sub-100 nm crosslinked polythioether nanoparticles were synthesized via thiol-ene photopolymerization in miniemulsion using high-energy homogenization [65].…”

“…Their synthesis was performed in water, at ambient temperature, and without the use of any organic solvent. The resultant linear poly (thioether ester) particles had an average diameter of 130 nm [68].…”

Biocompatible Polymeric Nanoparticles From Castor Oil Derivatives via Thiol‐Ene Miniemulsion Polymerization

“…[13] Apart from the advantages already mentioned, thiol-ene reactions allow the synthesis of high molecular weight polyesters in aqueous dispersed medium and are thus suitable for the production of polymeric nanoparticles containing ester groups in the main chain, which can undergo hydrolysis, enabling their degradation in physiological environment, which is of great importance for biomedical applications or material disposal. [14][15][16] Besides avoiding the use of organic solvents, miniemulsion polymerization offers advantages over other types of polymerization, such as bulk and solution polymerizations, because it yields products with low viscosity and therefore mass, heat, and momentum transfer is improved. Additionally, the miniemulsion process enables the production of polymeric nanoparticles with unique characteristics and vast commercial interest.…”

“…[16][17][18][19][20][21] Thiol-ene step-growth polymerization in miniemulsion is currently being investigated and only a handful of articles have been published in the literature. [14][15][16][22][23][24] Furthermore, works portraying the polymerization of renewable monomers through thiol-ene polymerization in aqueous dispersed medium are still uncommon. [16] In this work, we present the synthesis and characterization of poly(thioether-ester) nanoparticles via thiol-ene polymerization in miniemulsion using a fully renewable α,ω-diene monomer obtained from 10-undecenoic acid and 1,3-propanediol, both derived from castor oil.…”

An orthogonal, one-pot, simultaneous UV-mediated route to thiol-ene/sol-gel film

“…The last feature refers to the fact that this coupling reaction can be 'orthogonal' to a broad array of reagents, solvents, and functional groups. Thiol-ene orthogonality [3] has already paved the way for step-growth polymerizations and chain functionalizations performed in a wide range of chemical environments: aerated [4] and aqueous [5] conditions for example, or in the presence of biological [6] and complex [7] systems. The recent combination of thiol-ene with sol-gel chemistry provides another perfect illustration of this tolerance, because this inorganic polymerization process generally entails water and alcoholic solvents/byproducts, acid or base catalysts, and precursors bearing chloro or alkoxy hydrolyzable reactive groups [8].…”