Synthesis of poly(methyl methacrylate) via ARGET ATRP and study of the effect of solvents and temperatures on its polymerization kinetics

Abstract

This investigation reports the synthesis of poly(methyl methacrylate) via activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) and studies the effect of solvents and temperature on its polymerization kinetics. ARGET ATRP of methyl methacrylate (MMA) was carried out in different solvents and at different temperatures using CuBr 2 as catalyst in combination with N,N,N ′ ,N ″ ,N ″ -pentamethyldiethylenetriamine as a ligand. Methyl 2-chloro propionate was used as ATRP initiator and ascorbic acid was used as a reducing agent in the ARGET ATRP of MMA. The conversion was measured gravimetrically. The semilogarithmic plot of monomer conversion versus time was found to be linear, indicating that the polymerization follows first-order kinetics. The linear polymerization kinetic plot also indicates the controlled nature of the polymerization. N,N-Dimethylformamide (DMF), tetrahydrofuran (THF), toluene, and methyl ethyl ketone were used as solvents to study the effect on the polymerization kinetics. The effect of temperature on the kinetics of the polymerization was also studied at various temperatures. It has been observed that polymerization followed first-order kinetics in every case. The rate of polymerization was found to be highest (k app = 6.94 × 10 −3 min −1 ) at a fixed temperature when DMF was used as solvent. Activation energies for ARGET ATRP of MMA were also calculated using the Arrhenius equation. K E Y W O R D Satom transfer radical polymerization, kinetics, methyl methacrylate, solvent effect

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

“…Generally, the most common solvents are those able to simultaneously dissolve many monomers and their polymers as a condition of maintaining good control over polymerization and keeping the system homogenous throughout the entire synthesis. Frequently, the role of the polymerization solvent is played by aprotic DMF, 13,25,27,43 toluene, 44,45 tetrahydrofurane 25,46 and DMSO [47][48][49] or protic methanol 15,48 or anisole. 15,47 Even though these organic solvents are far from perfect, considering their hazardous impact on the environment, they continue to be widely used in RDRP techniques, which is presented in Chart 1.…”

“…In a typical ATRP system, transition metals' halides, such as copper 9,10,23,24,43,45,63,67,75,135 or iron 5,22,[25][26][27]60 bromides are added due to their ability to complex various compounds containing electron-donating groupsligands, which together form a catalyst complex, necessary to conduct the polymerization. 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.…”

“…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. 15,44,52,60,63,74,91,175,176 From all the above-mentioned discussion, ARGET ATRP may be considered the most accessible and probable to scale up to a semi-industrial scale due to its low energy consumption, high resistance to oxygen, enabling synthesis in open-toair systems 9,11,74,177,178 as well as a wide variety of reducing factors used, providing ample opportunities...…”

“…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 ( e ATRP), 70,103,137,164–166 photochemically induced ATRP (photo-ATRP), 5,43,64,72,76,111 mechanically controlled ATRP (mechano-ATRP) 167,168 or ultrasound-mediated ATRP (sono-ATRP) 169–173 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. 15,44,52,60,63,74,91,175,176…”

Poly(methyl methacrylate) modified Starch: their preparations, properties and applications

“…Among the different methacrylate monomers, methyl methacrylate (MMA) is the most commercially used monomer. It is capable to undergo polymerization by different polymerization methods [41,42] . The homopolymer of MMA, poly(methyl methacrylate) (PMMA) finds many applications in various fields e.g., in drug delivery [42] , bone cement [43] , tissue engineering [44] , as electrolytes [45] , in molecule separation [46] , in conductive polymer matrix [47,48] , in photonic devices [49] , in solar devices [47] .…”