The role of donor-acceptor complexes in polymerization

Radical copolymerisation of chlorotrifluoroethylene with isobutyl vinyl ether initiated by the persistent perfluoro-3-ethyl-2,4-dimethyl-3-pentyl radical

“…Of these possible addition pathways, path 1a is considered the most likely as the highly electrophilic •CF 3 radicals should preferentially attack the most electron donating, least hindered site in the monomer mixture 10,[21][22][23] . In the case of the vinyl ether, known to be a donating monomer 24 , the preferred site will be the CH 2 carbon, as it is not sterically hindered and is electron rich.…”

Modern aspects of quantitative theory of free-radical copolymerization

“…The corresponding kinetic scheme of the propagation reaction parallel with reactions (2.1) involves four additional ones [36]: which together with equilibrium constant k complex formation, comprise a complete set of parameters of such a kinetic model. Up-to-now, a whole range of radical copolymerization processes has been studied for which the formation of the complex between the monomers plays a key role [37,38]. The concentration M12 of M1 ... Mz complex is determined by the nature of the monomers.…”

“…In contrast to the above mentioned models, the similar statistical description of the products of the complex-radical copolymerization occurring through the scheme (2.5) has been carried out quite recently [37,49,[55][56][57][58][59][60]. Within the framework of this Seiner-Litt model, both copolymer composition [37,49,[55][56][57][58] and fractions of the different triads and blocks of the monomer units in the macromotecutes were calculated [57].…”

“…Within the framework of this Seiner-Litt model, both copolymer composition [37,49,[55][56][57][58] and fractions of the different triads and blocks of the monomer units in the macromotecutes were calculated [57]. The probability approaches which were applied in these works, are regarded as being of limited applicability in contrast to the general statistical method [49,59,60].…”

“…The substitution of the transition probabilities (3.18) into these relationships results in a well-known expression derived quite differently by Seiner and Litt [37]. This expression connects the instantaneous copolymer composition with the current concentrations of the monomers and their complex.…”