The Kinetics of the Three-dimensional Photopolymerization of Some Diacrylates

Kinetic model of block photopolymerization of glycidyl methacrylate to high conversion

“…Linear chain termination plays the role of an active radical self-burial act observed in computer experiments accordingly to the theory of self-avoiding walks. 27,28 The obtained kinetic equations for stationary and nonstationary (so-called postpolymerization) processes, 25,26 both qualitatively, explain all the main peculiarities of block 3D polymerization to high conversion and also were quantitatively proved on a wide range of experimental materials in regard to the kinetics of photoinitiated polymerization of dimethacrylates. This permitted, for the first time, a numerical estimate of the constant rates of linear chain termination.…”

“…[23][24][25][26] The starting principles include that the observed rate of polymerization is a sum consisting of the rate of the homophase process proceeding in a volume of a liquid monomer according to a classic kinetic scheme with the quadratic chain termination and the rate of the heterophase process proceeding under gel-effect conditions; clusters of a solid polymer in a liquid monomeric phase and clusters of a liquid monomer in a solid polymeric matrix are characterized by the structure of mass fractals; and the gel effect in the interface layer decreases the rate of chain termination and the transition of control under it up to chain propagation rate. Linear chain termination plays the role of an active radical self-burial act observed in computer experiments accordingly to the theory of self-avoiding walks.…”