Dimensional Optimization for ZnO-Based Mechano-ATRP with Extraordinary Activity

Abstract

Various piezoelectric nanomaterials were utilized in ultrasound-mediated atom transfer radical polymerization (ATRP), owing to their outstanding piezoelectric effect. However, the relationship between the morphology of those piezocatalysts and polymerization has not been clearly established. Herein, we employed different piezoelectric zinc oxide (ZnO) nanomaterials to achieve novel mechano-induced ATRP (mechano-ATRP). Based on the synergistic effect of piezoelectric properties and specific surface area, the catalytic activity of 1D ZnO nanorods (1D-ZnO NRs) with increased aspect ratio outperformed that of 0D ZnO nanoparticles (0D-ZnO NPs). Compared to the conventional ATRP system, this system exhibited extraordinary activity toward the less activated monomer acrylonitrile (67% conversion after 6 h), with a narrow molecular weight distribution (polydispersity index ∼ 1.19). Furthermore, implications of ZnO loading, copper salt amount, degree of polymerization, monomer, and solvent were also studied for the highly efficient mechano-ATRP.

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

“…Concerning current developments of ATRP, regarding the decrease in the concentration of catalytic complex 64,76,77,161 or its overall elimination, 49,98,102,162 many researchers are focused on the search of efficient yet low-cost and ecological reducing factors, enabling constant regeneration of activator thorough the reaction and thus employing only ppm amounts of catalyst. 23,64,76,77,163 Depending on the type of reducing factor used, various techniques of ATRP might be distinguished starting with electrochemically mediated ATRP (eATRP), 70,103,137,[164][165][166] photochemically induced ATRP ( photo-ATRP), 5,43,64,72,76,111 mechanically controlled ATRP (mechano-ATRP) 167,168 or ultrasound-mediated ATRP (sono-ATRP) [169][170][171][172][173] employing external reductors, followed by methods applying compounds present in reaction mixtures, such as zero-valent metals in SARA ATRP 10,48,67,132,174 or chemical substance in Activators Regenerated by Electron Transfer (ARGET) ATRP. 15,44,52,60,63,…”

Polymer-modified regenerated cellulose membranes: following the atom transfer radical polymerization concepts consistent with the principles of green chemistry

“…Low catalyst loading methods offer more environmentally benign and industrially scalable reaction conditions compared to "classical" ATRP but also provide an option to prepare polymers with designed dispersity, defined by the catalyst content (Discekici et al 2018(Discekici et al , 2016(Discekici et al , 2017Lu et al 2019;Matyjaszewski 2012a;Parkatzidis et al 2020;Treat et al 2014). The new low ppm ATRP methods regenerate the activator by the use of a chemical reducing agent as a radical initiator in initiators for continuous activator regeneration (ICAR) ATRP (Konkolewicz et al 2012;Luan et al 2022), chemical compounds (Luo et al 2022;Matyjaszewski et al 2007;Min et al 2007) and silver (Williams et al 2015) in activators regenerated by electron transfer (ARGET) ATRP-used a few times for membrane modification (Bhut et al 2012;Worthley et al 2011), zerovalent metals in supplemental activator and reducing agent (SARA) ATRP (Chmielarz et al 2015a;Konkolewicz et al 2014Konkolewicz et al , 2013, external stimuli as an electrical current in electrochemically mediated ATRP (eATRP) (Chmielarz 2017;Chmielarz et al 2015b;De Bon et al 2022;Han et al 2022;Park et al 2015;Zhao et al 2022), light in metal-free (Soly et al 2022;Su et al 2022;Treat et al 2014) or photochemically mediated ATRP (photo-ATRP) (Fu et al 2021;Huang et al 2017;Tasdelen et al 2011), mechanical forces in mechanically induced ATRP (mechano-ATRP) (Liu et al 2022a;Mohapatra et al 2018;Wang et al 2019), ultrasound in ultrasonication-induced atom tran...…”

“…Therefore, the main direction of research for cellulose membranes modification by controlled polymerization is the use of ATRP techniques with a reduced catalyst concentration. Development should focus mainly on concepts controlled by external factors, such as electric current (Chmielarz et al 2017a;Luo et al 2021;Zaborniak et al 2020a;Zhao et al 2021), ultrasound (Liu et al 2022a;Mohapatra et al 2017;Zaborniak and Chmielarz 2019a, b) and light (Corbin and Miyake 2022;Liu et al 2020;Wei et al 2022;Xu et al 2022;Yan et al 2020;Zaborniak et al 2020b). Among externally controlled methods, light-triggered ATRP besides simple experimental setup, mild conditions with limited side reactions, easily accessible and tunable external stimuli source, and temporal control is the only externally controlled approach providing a metal-free catalyst system (Bian et al 2019;Corbin and Miyake 2022;Discekici et al 2016;Treat et al 2014;Xu et al 2021;Zhou et al 2022Zhou et al , 2020.…”

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

“…In order to reduce the amount of catalytic complex used in “normal” ATRP, a few variants of ATRP have been developed taking into account the use of internal (chemical) or external reducing factor. The most common external factors for continuous reduction a deactivator Cu(II) to an activator Cu(I) species are: electric current in electrochemically‐mediated ATRP ( e ATRP), 6 light in photoinduced ATRP (photo‐ATRP), 7 ultrasonic waves in ultrasonication‐induced ATRP (sono‐ATRP) 8 and mechanical forces in mechanically induced ATRP (mechano‐ATRP) 9 . In the case of chemical reductors, Cu 0 wire/sponge/powder is used in supplemental activator and reducing agent (SARA) ATRP, 10 however ascorbic acid (AsAc), 11 tin(II) 2‐ethylhexanoate, 12 glucose, 13 Ag 0 14 or even alcohols 15 used in activator (re)generated by electron transfer (A(R)GET) ATRP work equally well.…”

“…The most common external factors for continuous reduction a deactivator Cu(II) to an activator Cu(I) species are: electric current in electrochemicallymediated ATRP (eATRP), 6 light in photoinduced ATRP (photo-ATRP), 7 ultrasonic waves in ultrasonicationinduced ATRP (sono-ATRP) 8 and mechanical forces in mechanically induced ATRP (mechano-ATRP). 9 In the case of chemical reductors, Cu 0 wire/sponge/powder is used in supplemental activator and reducing agent (SARA) ATRP, 10 however ascorbic acid (AsAc), 11 tin(II) 2-ethylhexanoate, 12 glucose, 13 Ag 0 14 or even alcohols 15 used in activator (re)generated by electron transfer (A(R) GET) ATRP work equally well. Cyclic catalyst regeneration result in the reduction of concentrations of the catalytic complex even to ppb level.…”