The Oxidative Polymerization of Vinyl Monomers in the Presence of N‐Hydroxyphthalimide

Abstract

The oxidation of vinyl compounds such as styrene, α‐methylstyrene, methyl methacrylate, acrylonitrile with molecular oxygen in the presence of N‐hydroxyphthalimide have been studied. It was shown that the N‐hydroxyphthalimide is efficient in initiation of the oxidative polymerization of vinyl monomers. The products of the monomer oxidation at 66 °C and 1 atm of O2 are corresponding polyperoxides and low molecular carbonyl compounds. IR‐ and 1H NMR spectroscopy confirm the alternating copolymer structure of polyperoxides with –O–O– bonds in the main chain. In the oxidative polymerization of vinyl monomers initiated with the mixtures of N‐hydroxyphthalimide and 2,2′‐azobisisobutyronitrile or benzoyl peroxide it was observed a synergistic effect of initiators’ action. N‐hydroxyphthalimide reacts with molecular oxygen, initiator radicals or monomer to form the phthalimide‐N‐oxyl radical, which participates in the chain initiation stage and does not participate in the termination stages, which leads to a synergistic effect.

An Investigation on the Effect of N-Hydroxyphthalimde and Supercritical Carbon Dioxide on the Peroxide Degradation of Polypropylene

“…This would also be a clear deviation from the starting material, and so it cannot be said that grafting has occurred, at least within the experimental detection limit of FT-IR (about 1%). This is not surprising as Opeida et al already noted this before (Opeida et al, 2019).…”

“…During the last 3 decades, N-hydroxyphthalimide (NHPI) has been receiving a moderate amount of attention in literature, with particular interest into its function as organic catalyst for oxidation reactions (Hara et Opeida et al, 2019). The operating mechanism is to generate the phthalimide-N-oxyl radical (PINO) from NHPI.…”

Kinetics of N-oxyl Radicals’ Decay

“…We can assume the formation of molecular complexes (solvates) between the PINO radical and solvent molecule. Their formation will be facilitated by the large dipole moment of PINO and its electrophilic character. ,,, The higher the value of the solvent donor number, the larger the degree of the PINO solvation, which prevents its spontaneous decay.…”

Recent Advances in N‐Hyrdoxypthalimide: As a Free Radical Initiator and its Applications

“…The various vinyl compounds like methyl methacrylate, acrylonitrile, styrene and α‐methylstyrene were taken into consideration for oxidation reaction study. The structures of polyperoxides and carbonyl compounds formed were confirmed by IR and 1 H NMR spectroscopy [95] . Witek and team synthesized poly(HEA‐co‐DVB) which was immobilised by NHPI as catalyst under oxidative conditions.…”

“…The structures of polyperoxides and carbonyl compounds formed were confirmed by IR and 1 H NMR spectroscopy. [95] Witek and team synthesized poly(HEA-co-DVB) which was immobilised by NHPI as catalyst under oxidative conditions. The synthesized polymeric support and poly(HEA-co-DVB)/NHPI were characterized by various spectroscopic techniques.…”