Coffee Beverage: A New Strategy for the Synthesis of Polymethacrylates via ATRP

Abstract

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.

From non-conventional ideas to multifunctional solvents inspired by green chemistry: fancy or sustainable macromolecular chemistry?

“…65,66 In many cases, the occurring side reactions decrease the control over the process, resulting in high dispersity 16,49 and low initiation efficiency. [67][68][69] However, some techniques are progressing to overcome those setbacks to create more environmentally friendly processes, able to be implemented on a larger scale. An excellent example would be employing oxygen scavengers such as glucose oxidase 36,70 to conduct syntheses in air conditions, 9,27,43,48,[70][71][72][73][74][75] using catalysts characterized by high activity, e.g.…”

“…Additionally, in the last 20 years, it was revealed that many compounds might play a dual role in the polymerization mechanism. For example N-phenylphenothiazine as photocatalyst and oxygen scavenger, 73 2-(dimethylamino)ethyl methacrylate as the monomer and internal reducing factor, 11,69 nitrogen-based ligands as reducing factors 72,[104][105][106] or non-conventional solvents containing various types of 'impurities' playing important roles in the RDRP mechanism (Fig. 2).…”

“…The most commonly used ones are complexes of Cu II Br 2 with amine ligands such as 2,2′-bipyridine (BPY), 48,[136][137][138] N,N,N′,N′,N″-pentamethyldiethylenetriamine (PMDETA), 15,43,44,71,132 tris(2-(dimethylamino)ethyl)amine (Me 6 TREN), 8,14,23,65,126,127,139 or [(2-pyridyl)methyl]amine (TPMA). 11,47,64,65,69,70,75,76,132,136 However, in the case of ironmediated systems with phosphines e.g. tris(2,4,6-trimethoxyphenyl)-phosphine (TTMPP) were also employed.…”

Red is the new green: Dry wine‐based miniemulsion as eco‐friendly reaction medium for sustainable atom transfer radical polymerization

“…The concept of using alcoholic beverages including flavored Bison Grass Vodka as a reaction medium has been successfully demonstrated for the blue‐light‐assisted synthesis of PDMAEMA brushes, 26 but still no such solution has been presented for non‐water miscible monomers. For example, an attempt was made to synthesize P n BA in coffee extract‐based miniemulsion, however the synthesized polymers were characterized by a wide molecular weight distribution ( Ð = 3.07), which suggested an uncontrolled polymerization 27 . Herein, an environmentally friendly synthetic system using functional wine‐based miniemulsion as a reaction medium for the low ppm ATRP (~300 ppm by wt of Cu II /tris(2‐pyridylmethyl)amine [TPMA]) of hydrophobic (meth)acrylates is presented for the first time.…”

“…For example, an attempt was made to synthesize PnBA in coffee extract-based miniemulsion, however the synthesized polymers were characterized by a wide molecular weight distribution (Ð = 3.07), which suggested an uncontrolled polymerization. 27 Herein, an environmentally friendly synthetic system using functional winebased miniemulsion as a reaction medium for the low ppm ATRP ($300 ppm by wt of Cu II /tris(2-pyridylmethyl)amine [TPMA]) of hydrophobic (meth)acrylates is presented for the first time.…”