Synthesis and polymerization of polyacrylic esters

Abstract The method of telomerization has been employed in the synthesis of the telomer homologs of polyacrylate esters with successively increasing degrees of polymerization ( n ) and of telomers differing in the nature of the polyester chain. Compounds have been synthesized of the general formula magnified image where R and R 1 are alkyl or aryl radicals and n = 2, 4, 8, and 20. With changes in ( n ) from 2 to 20 the structural viscosity of the polyacrylate esters increased from 150 to 8000 centistokes (at 20°), the specific gravity from 1.213 to 1.308, and n D 20 from 1.515 to 1.5479. The presence of double bonds in the molecules of the polyacrylate esters synthesixed made it possible to carry out their polymerization (hardening) in the presence of radical chain initiators with the formation of glassy or elastic, insoluble, nonmelting polymers of sufficient thermal stability and endowed with a number of valuable properties so as to be of considerable practical potentiality. The changes in physical properties of the reaction system (gelation, gradual increase in density and finally the formation of a glass structure) in the course of the polymerization beginning from the very early stages (the gelation point is reached at 5–10% conversion) are responsible for a number of specificities in the kinetics of the hardening of polyacrylate esters. Owing to this we undertook a detailed investigation of the polymerization kinetics under widely varying conditions. Polymerization in bulk takes place autocatalytically, since with increasing degree of structuration in the course of polymerization the rate of diffusion of free radical diminished, leading to a decrease in rate of chain termination. The rate of reaction begins to diminish markedly only at large extents of polymerization. A study has been made of the effect of diluting the reaction mixture with an inert solvent, of the initiation rate, nature of the initiating agent, temperature, chemical structure of the initial polyacrylate ester, as well as of the addition of inhibiting agents on the polymerization kinetics. The results obtained have been discussed from the standpoint of the capacity of the system for structuration under the various conditions of reaction. The heats of hardening of the polyacrylate esters with successively increasing distance between their values have been discussed with respect to the reaction mechanism.