Solid-phase polymerizations at high pressures

The following compounds have been found to polymerize spontaneously in the solid state at pressures in the range 10-50 kbar, at temperatures between 20 and 200°C: acrylamide, p-phenylstyrene, potassium p-styrenesulphonate, itaconic anhydride, maleic anhydride, maleimide, 1,2,3,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic anhydride, acenaphthylene, p-benzoquinone, N,N' -p-phenylene-dimaleimide, sulpholene, diphenylacetylene, 8-trioxan. The pressure-temperature requirements for polymerization have been determined in a high-pressure "squeezer" apparatus and in a diamond optical cell which permits infrared spectral analysis of a specimen while it is under compression. Apart from diphenylacetylene and trioxan, the compounds that polymerized were either monosubstituted ethylenes or cyclic 1,2-disubstituted ethylenes. Non-cyclic 1,2-disubstituted ethylenes and tri-substituted and tetra-substituted ethylenes failed to polymerize. There is evidence that shearing stresses played a part in some of the reactions. 1-Allyl-2-thiourea did not polymerize, but transformed from its stable crystal form I to the unstable modification 11.