Triple‐functional riboflavin‐based macromolecule was synthesized providing an efficient activator regeneration by electron transfer atom transfer radical polymerization of butyl acrylate in a miniemulsion media in a fully oxygen tolerant environment. For the first time, the riboflavin‐inspired supramolecular structure fulfilled three primarily roles, acting simultaneously as (a) an initiator due to incorporation of bromine molecules in a ribitol tail by esterification reaction of riboflavin with α‐bromoisobutyryl bromide; (b) a reducing agent caused by the preservation of redox functionality of isoalloxazine ring in this structure; (c) and enables polymerization in air conditions. Electrochemical characterization of the riboflavin‐based molecule was conducted by a series of cyclic voltammetry measurements, determining an activation rate constant (ka = [1.34 ± 0.58] × 103 M−1 s−1) reflecting a reduction of the copper(II) catalytic complex in the presence of the multifunctional initiator. Proposed reaction system allowed to maintain control during polymerization proved by linear kinetics and a clear shift in molecular weights, resulting in the preparation of polymer brushes with narrow molecular weight distribution (Mw/Mn = 1.39) with high initiation efficiency (ƒi = 72%).

The novel hydrophobic coating material was received for the first time by a two-step synthetic route. Firstly, the 15-functional brominated macroinitiator was prepared by the esterification methodology. Next step covers synthesis of star-like polymers by poly(n-butyl acrylate) (PBA) arms polymerization via three low-ppm atom transfer radical polymerization (ATRP) approaches including application of copper and silver wire in SARA and ARGET ATRP, respectively, as driving forces in redox cycle of catalyst, and an external stimulus in the form of electric current (seATRP) as the third approach in copper(II) regeneration system. As expected, the electrochemically mediated technique allows synthesis of tannic acid-inspired coating polymers in precisely controlled manner during the entire polymerization process, proved by linear firstorder kinetics plot in contrast to above-mentioned methods, low dispersity (Ð = 1.18) of star-shaped polymers, and high efficiency of initiation (ƒ i = 81%) determined after detaching of polymers side arms. Macromolecules received by all low-ppm ATRP solutions were characterized by preserved chain-end functionality (theoretical dead chain fraction; DCF theo <1%). Adhesive and hydrophobic properties of received polymer materials were investigated by contact angles (θ) and free surface energy (FSE) calculations. Prepared polymer films besides excellent hydrophobic properties have great potential as a self-healing solution. K E Y W O R D S hydrophobic surfaces, low-ppm ATRP, tannic acid-based coating materials 1 | INTRODUCTION Recent needs in the field of protective coatings with increased hydrophobicity and functional bioactive surfaces permanently connected with naturally derived substrates gain more attention, and therefore are a driving force in searching for innovative polymeric biomaterials, with emphasis on receiving coating materials, which perfectly cooperate with the tissues of the human body. The effective approach in the synthesis of functional biomaterials surfaces is grafting adhesive substances of natural origin with monomers characterized by appropriate properties (eg, vinyl monomers). 1-5 In this field of biocoatings, investigation of polyphenol chemistry in materials science could be an indication of the appropriate naturally derived substrate with desired adhesive properties.Considering the polymeric coatings, poly(n-butyl acrylate) (PBA) deserves attention. Incorporate itself increases the hydrophobicity of received surfaces; 6 moreover, it is thoroughly investigated in the context of controlled polymerization technique. 7-9 Due to this fact, it is simple to receive precisely controlled polymeric materials; therefore, PBA constitutes a suitable block to incorporate the next functional segment in a polymeric coating material, 8-10 contributing in addition to hydrophobicity also excellent resistance for weather conditions 11,12 and low temperature performance. 13 Recently, PBA was investigated as an excellent soft block, which bears the reversible moieties. This

Ultrasound‐mediated atom transfer radical polymerization (sono‐ATRP) in miniemulsion media is used for the first time for the preparation of complex macromolecular architectures by a facile two‐step synthetic route. Initially, esterification reaction of sucrose or lactulose with α‐bromoisobutyryl bromide (BriBBr) is conducted to receive multifunctional ATRP macroinitiators with 8 initiation sites, followed by polymerization of n‐butyl acrylate (BA) forming arms of the star‐like polymers. The brominated lactulose‐based molecule was examined as an ATRP initiator by determining the activation rate constant (ka) of the catalytic process in the presence of a copper(II) bromide/tris(2‐pyridylmethyl)amine (CuIIBr2/TPMA) catalyst in both organic solvent and for the first time in miniemulsion media, resulting in ka = (1.03 ± 0.01) × 104 M−1 s−1 and ka = (1.16 ± 0.56) × 103 M−1 s−1, respectively. Star‐like macromolecules with a sucrose or lactulose core and poly(n‐butyl acrylate) (PBA) arms were successfully received using different catalyst concentration. Linear kinetics and a well‐defined structure of synthesized polymers reflected by narrow molecular weight distribution (Mw/Mn = 1.46) indicated 105 ppm wt of catalyst loading as concentration to maintain controlled manner of polymerization process. 1H NMR analysis confirms the formation of new sugar‐inspired star‐shaped polymers.

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.

Coffee, the most popular beverage in the 21st century society, was tested as a reaction environment for activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) without an additional reducing agent. Two blends were selected: pure Arabica beans and a proportional blend of Arabica and Robusta beans. The use of the solution received from the mixture with Robusta obtained a high molecular weight polymer product in a short time while maintaining a controlled structure of the synthesized product. Various monomers with hydrophilic characteristics, i.e., 2-(dimethylamino)ethyl methacrylate (DMAEMA), oligo(ethylene glycol) methyl ether methacrylate (OEGMA500), and glycidyl methacrylate (GMA), were polymerized. The proposed concept was carried out at different concentrations of coffee grounds, followed by the determination of the molar concentration of caffeine in applied beverages using DPV and HPLC techniques.