The monograph is intended for elucidation of the novel trend in chemical
physics regarding the polymer non-crystalline phase. It stresses the physical
phenomena affecting the kinetics and mechanism of chemical reactions proceeding
in the non-crystalline polymer matrix (NCPM). NCPM is depicted in terms of a
supramolecular (carcass-micellar) model. The model is thought to reflect
heterophase packing of polymeric chains, which co-operate as a molecular-chain
sponge. The NCPM model presented is proved for adequate description of
principal structure-physical phenomena to elaborate the scheme of structural-
kinetic modeling of chemical reactions in bulky polymers. Structure-physical
phenomena elucidated in the monograph are: - peculiarities of polymer
plasticization and polymer blending with liquids; - structural and
thermodynamic aspects of sorption of low molecular species; - properties of ESR
(spin) probes and optical (molecular) probes; - features of water absorbed by
polymers; - mechanical and thermal effects generated by the molecular-chain
sponge; - supramolecular aspects of NCPM chemical physics. This monograph
includes the structural-kinetic modeling of complex polymer chemical reactions.
It deals with the problem of mechanism and kinetics of free radical chain
reactions using thermal and photochemical model reactions of dibenzoyl peroxide
with glassy-like polymers (cellulose triacetate, polycarbonate, polystyrene,
polyamide PA-548), viscoelastic polymers (atactic polypropylene, polyamide PA-
548, polyethylene, polyisobutylene, melted poly(ethylene oxide), and isotactic
polypropylene. In all cases, the supramolecular heterophase mechanism of the
processes, which was unknown forhomogeneous systems, was proved. Furthermore,
heterophase mechanisms of photochemical reaction between naphthalene and
cellulose triacetate and photolysis of poly(methyl methacrylate) proceeding as
a photochain reaction are indicated.
