Several properties of propagating fronts of addition polymerization were studied. A power function could be fit to the velocity dependence on initiator concentration, but not with the exponents predicted by current models or in agreement with other published work. Bubbles from the volatile by‐products of initiator decomposition were found to affect the front velocity and curvature. The front velocity for triethylene glycol dimethacrylate polymerization was found to depend linearly on temperature over a moderate range. The conversion of methacrylic acid in fronts varied greatly with initiator type and concentration. Benzoyl peroxide produced much lower conversion than t‐butyl peroxide, but fronts with tBPO propagated slower. A dual initiator system of BPO and tBPO produced rapidly propagating fronts with good conversion but the contribution of each initiator to the velocity was not additive. The possibility of chain branching was considered. The apparent molecular weight distributions were very broad, often trimodal, and found to depend on initiator type and concentration as well as the tube diameter. The temperature profiles were measured and found to be very sharp for BPO and broader for tBPO but both had front temperatures in excess of 200°C, indicating a high ceiling temperature. © 1995 John Wiley & Sons, Inc.

Polymerization and characterization of polyacrylamide prepared by frontal polymerization are described. Frontally polymerized polyacrylamide is imidized and crosslinked during polymerization. Imide formation was determined by elemental analysis. The addition of commercial polyacrylamide or barium carbonate to the monomer (acrylamide) and initiator (potassium persulfate) decreased the reaction temperature from 235 °C to < 100 °C, thereby reducing imide formation. The commercial polyacrylamide‐diluted product, frontally polymerized polyacrylamide‐diluted product, and the barium carbonate‐diluted product were characterized by IR, TGA, and elemental analysis. Molecular weights of barium carbonate‐diluted samples were determined by light scattering and found to be on the order of one million. Conversion of the barium carbonate‐diluted product was determined to be 76 ± 6%, independent of the amount of diluent over the range 0.8:1–1.5:1. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1129–1135, 2000

We demonstrate for the first time spherically propagating frontal polymerization that also exhibits spin modes. We have developed an interesting system using the amine-catalyzed Michael addition of a trithiol to a triacrylate to create a rubbery gel. The gel suppresses convection and bubble formation during front propagation. A peroxide is also present to act as a thermal initiator. The front propagates via free-radical polymerization of the remaining triacrylate after being initiated photochemically in the center of the reactor. It is possible to prepare the rubbery gel in any shape and then initiate thermal frontal polymerization. So-called spin modes have been observed for the first time in spherically propagating fronts in which waves of polymerization propagate on the expanding spherical front. A system using a diacrylate dissolved in dimethyl sulfoxide with added silica gel and with persulfate as the initiator supports spherical fronts but does not exhibit spin modes.

Tschuikow-Roux, E.; Rauk, A. J. Phys. Chem. 1991, 95,9832. (b) Chen, Y.; Rauk, A.; Tschuikow-Roux, E. J. Phys. Chem. 1991, 95.9900. (1 5) Pople, J. A.; Head-Gordon, M.; Fox, D. J.; Raghavachari, K.; Curtis, (16) Corbett, P.; Tarr, A. M.; Whittle, E.A manganese-catalyzed Belousov-Zhabotinskii (BZ) reaction with a mixed hypophosphite/acetone substrate was found to be remarkably sensitive to stirring in a batch reactor. The reaction d a t e d in a container with a gas/liquid interface (either air or nitrogen). However, when the reaction was stirred in a sealed flask with no interface, the system remained in the reduced state. When the slow stirring (about 100 rpm) was stopped, a pink color from Mn(II1) was observed to ascend from the Teflon-coated stir bar. When a glass stir bar was used, the system would oxidize much more slowly than with the Teflon one. A possible mechanism is considered in which bromine loss to the gas phase is crucial for oscillation. In the sealed system, oxidation occurs when the stirring is stopped because bromine can adsorb to the surface of the Teflon, allowing local oxidation which spreads throughout the system.

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