The influence of small additives of cobalt(II) porphyrin (Co II Pn) on cross linking radical polymerization of butane 1,4 diol dimethacrylate and its structural analog butane 1,4 diol diacrylate was studied. The kinetics of cross linking radical polymerization of di(meth)acrylates in the absence and presence of Co II Pn and the diffusional sorption and physical mechanical properties of the resulting polymers were studied. Cobalt(II) porphyrin decreases substantially the polymerization rate and partially suppresses the gel effect. Diacrylate polymerization in the presence of Co II Pn proceeds with an induction period, whose value is determined by the content of Co II Pn. Cobalt(II) porphyrin modifies the structure and properties of the formed cross linked polymers. In the case of dimethacrylate, this is caused by the catalytic chain transfer reaction, whereas for diacrylate the reason is the reversible inhibition reaction.In cross linking radical polymerization of polyfunc tional monomers, the growth of linear chains bearing "pen dant" double bonds is accompanied by intramolecular cyclization and intermolecular and intramolecular cross linking in branched macromolecules, microgel particles, and macrogel. 1,2 As a result, special topological (small cycles) and morphological (microgel particles, grains) structures are formed in the polymer, and the cross linked polymer formed is characterized by a high degree of struc tural heterogeneity. 1,2 The process of structure formation of cross linked polymers can be controlled successfully by inhibitors of radical polymerization (nitro and nitroso compounds), 3 standard (thiols) 4,5 and catalytic (cobalt(II) macrocycles) 6-9 chain transfer agents, and agents of liv ing radical polymerization (alkoxyamines, transition metal complexes, iniferters). 10-12 The use of them makes it pos sible to control the contribution of reactions of polymer chain propagation, cyclization, and cross linking to the total conversion of C=C bonds.Cobalt(II) macrocycles based on porphyrin, phthalo cyanine, and cobaloxime demonstrate high efficiency as controlling additives. These compounds are widely used in radical polymerization of monofunctional mono mers to prepare oligomers or polymers with low degree of polymerization. 13,14 The main regularities of catalytic reactions that occur in the presence of the cobalt(II) macrocycles were established for vinyl monomers of dif ferent structure. 14 The radical polymerization of vinyl monomers with addition of cobalt(II) macrocycles, in particular, Co II Pn, is accompanied by the following re actions:where R n • , R m • , and R 1 • are radicals with degrees of polymerization of n, m, and 1, respectively; M is mono mer, HCo III Pn is hydride, Z n = is oligomer or polymer with the terminal double bond, and R n -Co III Pn is an active intermediate with the C-Co bond formed due to the reaction of the R n • radical with Co II Pn. Reac tions (1)-(2) are known as catalytic chain transfer, and reactions (3) and (4) are catalytic and reversible inhibi tions, resp...