Optical gradient materials produced via low-temperature isothermal frontal polymerization

Using a newly developed low-temperature frontal polymerization technique, poly(methyl methacrylate) (PMMA) matrices were prepared with nonuniform distributions of organic nonlinear optical dyes, with potential use as optical limiters. This technique affords lower temperature conditions than have been used before. A PMMA tube was filled with a dye, the initiator tert-butyl peroxide, and methyl methacrylate (MMA). Curing at 4°C resulted in a radial gradient of dye. An axial dye gradient was observed when MMA was overlaid and polymerization effected from a dye-doped PMMA seed using tricaprylmethyl ammonium persulfate as the initiator. In both cases, polymerization reactions were observed as a result of isothermal frontal polymerization with the subsequent formation of a nonlinear concentration distribution of the optical dye dopants. Low temperatures are desirable to eliminate thermal and photothermal degradation of temperature-sensitive dyes during the polymerization. The preparation of long polymer rods with organic dye gradients on the scale of several centimeters can also be realized with the use of low-temperature polymerization and the gradients controlled by the concentration of initiator. © 2001 John Wiley & Sons, Inc