Poor Solvents Improve Yield of Grafting-Through Radical Polymerization of OEO19MA.

Radical polymerization of poly(ethylene glycol) methyl ether methacrylate (OEO19MA, Mn ∼ 950) at an initial monomer concentration of 150 mM was investigated as a function of solvent composition. Conventional and controlled radical polymerizations in anisole at 60 °C converged at approximately the same equilibrium monomer concentration ([M]eq) of ∼38 mM, suggesting that livingness or diminished termination did not affect the thermodynamic parameters of polymerization. Conventional radical polymerizations (RPs) in anisole, dimethylformamide (DMF), toluene, and 1×PBS buffered water were taken to approximately 98% thermal initiator decomposition to determine [M]eq at reaction completion within a broad temperature range. The enthalpy (ΔHp) and entropy (ΔSp°) of polymerization were solvent-dependent. Polymerizations in 1×PBS were the most thermodynamically favorable, followed by those in DMF, toluene, and anisole. -ΔHp and -ΔSp increased with the square of the difference in the Hansen solubility parameters of poly(ethylene glycol) and the solvent. It is proposed that poor solvents favor polymer-polymer interactions over polymer-solvent interactions, which improves the thermodynamic polymerizability.

Mechanism of Supplemental Activator and Reducing Agent Atom Transfer Radical Polymerization Mediated by Inorganic Sulfites: Experimental Measurements and Kinetic Simulations.

The mechanism of atom transfer radical polymerization (ATRP) mediated by sodium dithionite (Na2S2O4), with CuIIBr2/Me6TREN as catalyst (Me6TREN: tris[2-(dimethylamino)ethyl]amine)) in ethanol/water mixtures, was investigated experimentally and by kinetic simulations. A kinetic model was proposed and the rate coefficients of the relevant reactions were measured. The kinetic model was validated by the agreement between experimental and simulated results. The results indicated that the polymerization followed the SARA ATRP mechanism, with a SO2•- radical anion derived from Na2S2O4, acting as both supplemental activator (SA) of alkyl halides and reducing agent (RA) for CuII/L to regenerate the main activator CuI/L. This is similar to the reversible-deactivation radical polymerization (RDRP) procedure conducted in the presence of Cu0. The electron transfer from SO2•-, to either CuIIBr2/Me6TREN or R-Br initiator, appears to follow an outer sphere electron transfer (OSET) process. The developed kinetic model was used to study the influence of targeted degree of polymerization, concentration of CuIIBr2/Me6TREN and solubility of Na2S2O4 on the level of polymerization control. The presence of small amounts of water in the polymerization mixtures slightly increased the reactivity of the CuI/L complex, but markedly increased the reactivity of sulfites.

Explaining unexpected data via competitive equilibria and processes in radical reactions with reversible deactivation.

In the game rock-paper-scissors, each of the three options, or pathways, has an equal chance of dominating, that is, rock beats scissors, scissors beats paper, and paper beats rock. In the classical form of the game, there is no one dominant pathway to follow, but they are all balanced in likelihood. However, in chemical reactions with several competing reagents, the question must be asked, are all competing reactions and pathways accessible? A related question is, if there are two, or more reversible processes that compete for the same reagent, will both processes equilibrate simultaneously, or will one process dominate system? Can these competing processes shed light on otherwise puzzling data? Several unexpected and counterintuitive experiments have been reported in radical reactions with reversible deactivation. These unexpected observations can be illustrated by the near absence of the products of conventional bimolecular radical coupling in the radical transformation of methylcobaltamine to acetylcobaltamine. Another counterintuitive observation is a difference in the copolymer composition in some copolymerizations proceeding via reversible-deactivation radical polymerization (RDRP) vs conventional radical polymerization (RP), for example, nitroxide mediated polymerization of styrene and methyl methacrylate. A similarly puzzling phenomenon is the reduction in the branching fraction in poly(acrylates) polymerized by RDRP vs conventional RP. In the three previously mentioned cases, the radicals formed in reversible deactivation radical reactions are identical to those formed in the corresponding conventional radical process; therefore an explanation for the discrepancy in the outcomes of the reaction is needed. Other unexpected observations include the presence of initial periods of slower monomer consumption in RDRP reactions initiated by a conventional radical initiator with certain chain transfer agents, while changing the nature of chain transfer agent can lead to an acceleration of the reaction during the initial period. Similarly, in Cu mediated atom transfer radical polymerization (ATRP) with initiators for continuous radical regeneration (ICAR) initiated by a conventional radical initiator, the rate of polymerization should not depend on either the alkyl halide concentration or the Cu concentration. However, experiments show that the rate could be 10 times faster with alkyl halide than without alkyl halide. Finally, in aqueous media, the presence of active alkyl halides can appear to stop the disproportionation of Cu(I) complexes. These unusual data point to a more complex mechanism than originally envisioned, and in fact all these counterintuitive observations can be explained by the concept of competing equilibria and processes. In these cases, the presence of two or more reactions competing for the same reagent typically causes one pathway to dominate, while the rate of the other pathways are diminished. Alternatively, the competing pathways and processes can cause one or more reversible or pseudoreversible reactions to be imbalanced and lead to products distinct from the case where rates of forward and reverse reactions are balanced. In this Account, the concept of competitive processes and equilibria is developed and used to explain each of the unusual observations highlighted above.

Encapsulation of ammonium molybdophosphate and zirconium phosphate in alginate matrix for the sorption of rubidium(I).

Ammonium molybdophosphate and Phozir (alone or in combination) have been encapsulated in alginate beads for the synthesis of rubidium sorbents. SEM and SEM-EDX analyses confirm the homogeneity of the sorbents in terms of composition and metal binding. AMP sorbent is less sensitive to pH than Phozir, and optimum pH is close to pH 3 for the binding of Rb(I). The Langmuir equation fitted well sorption isotherms and the maximum sorption capacities were in the range 0.65-0.74 mmol Rb g(-1). The resistance to intraparticle diffusion contributes to control uptake kinetics (effect of particle size) though the presence of solid inorganic particles reduces the impact of drying alginate capsules (preventing the collapse of the porous structure during the drying step). Breakthrough curves demonstrate the potential of these sorbents for the dynamic sorption of Rb(I) while using ammonium chloride (combined to nitric acid) allows recovering Rb(I) from loaded sorbents.