Low Ppm Atom Transfer Radical Polymerization in (Mini)Emulsion Systems

Abstract

In the last decade, unceasing interest in atom transfer radical polymerization (ATRP) has been noted, especially in aqueous dispersion systems. Emulsion or miniemulsion is a preferred environment for industrial polymerization due to easier heat dissipation and lower production costs associated with the use of water as a dispersant. The main purpose of this review is to summarize ATRP methods used in emulsion media with different variants of initiating systems. A comparison of a dual over single catalytic approache by interfacial and ion pair catalysis is presented. In addition, future development directions for these methods are suggested for better use in biomedical and electronics industries.

Principles and Characteristics of Polymerization-Induced Self-Assembly with Various Polymerization Techniques

“…Such methods are known as: simultaneous reverse and normal initiation (SR&NI)-ATRP; activators regenerated by electron transfer (ARGET)-ATRP; supplemental activators and reducing agent (SARA)-ATRP [also known as single-electron transfer living radical polymerization (SET-LRP)]; electrochemically mediated (e)-ATRP; and initiators for continuous activator regeneration (ICAR)-ATRP. 83 Another factor that potentially complicates ATRPISA is that both the activator and deactivator (Cu I -ligand and Cu II -ligand) need to be present in the growing nanoparticle core where the polymerization takes place. 80 Diffusion of these species into the nascent nanoparticle cores might be difficult, owing to its insoluble character.…”

Experimental Investigation of AGET ATRP Polymerization of Butyl Methacrylate in an Emulsion Stirred Tank Reactor

“…Fortunately, several ATRP initiation methods have been developed to reduce the cost of purifying the final product by using low concentration metal catalyst (Kreutzer, 2018;Shen et al, 2004;Surmacz and Chmielarz, 2020). The decrease of catalyst concentration is beneficial not only for economic and environmental perspectives, but also for minimizing catalyst side reactions with propagating radicals (Krys and Matyjeszewski, 2017).…”

“…Currently, progress has been made in polymerizing a number of polar monomers. The number of studies done on different CRP technique until 2020 is in the order ATRP>RAFT>NMRP, which indicates that ATRP is more popular than RAFT and NMRP techniques (Matyjaszewski, 2017;Surmacz and Chmielarz, 2020;Tsarevsky and Sumerlin, 2013).…”

“…Over the last three decades, significant improvement has been made either by increasing the catalytic activity of the Cu complexes or by recycling and recovering of the Cu complex. In most cases, about 100-200ppm of copper are still needed in regular ATRP (Surmacz and Chmielarz, 2020). In spite of the applauded research development in ATRP, availability of the best ligands for the preparation of highly active Cu catalyst are still lacking.…”

Sonochemistry-assisted photocontrolled atom transfer radical polymerization enabled by manganese carbonyl

“…Furthermore, ultrasound-mediated atom transfer radical polymerization was successfully performed in miniemulsion media, demonstrating the unique advantage of ultrasound in a heterogeneous reaction system. [48][49][50][51][52] We envisioned that the combination of light and ultrasound for activating Cu complexes that offer excellent control over ATRP would open up new possibilities for modulating the catalytic reactivity and the polymerization process.…”