Synthesis, characterization and reactivity of polymeric peroxides

Thermal degradation kinetics of para‐substituted poly (styrene peroxide)s in solution

“…In the degradation of poly(styrene peroxide) (PSP), these are competing processes. 2 The main products of the disproportionation pathway are ␣-hydroxy acetophenone, phenylglycol, and small quantities of phenyl glyoxal. In the unimolecular decomposition of PSP, which is a chain unzipping process, the macroalkoxy radicals undergo scission at the ␤-bond to the radical center, forming the carbonyl compounds benzaldehyde and formaldehyde.…”

“…1 The polyperoxides, which are alternating copolymers of the vinyl monomers and oxygen, find importance as polymeric thermal-, photo-, and base-catalyzed initiators for vinyl monomers to synthesize homopolymers, block, and comblike copolymers. 2 Most polymers degrade endothermally, whereas vinyl polyperoxides are an unique class of polymers that pyrolyze exothermally. 3 Further, their unique properties, such as auto-pyrolyzability and auto-combustibility, make them potential candidates for specialized fuels.…”

Degradable Polymers Prepared from Alkyl Sorbates and Oxygen under Atmospheric Conditions and Precise Evaluation of Their Thermal Properties

“…Occasionally decomposition rate increases during the reaction as seen in the autopyrolysis of peroxy compounds, which readily decompose via an exothermic process, namely, continue combustion even in an inert atmosphere. The synthesis and characterization of polymeric peroxides from many kinds of vinyl monomers have been carried out, [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24] since the first synthesis of a polymeric peroxide reported by Staudinger. 25,26 In general, however, many synthetic procedures for polymeric peroxides are accompanied by decomposition reactions due to the less stability of the polymers as the products.…”

“…For example, a peroxide polymer is formed in a high yield during the oxidative polymerization of styrene, but the simultaneous formation of benzaldehyde and formaldehyde is unavoidable and influences the polymerization kinetics and the reaction mechanism including a radical chain transfer. 8,12,27,28 The accurate evaluation of the thermal properties of peroxide polymers is often hin- dered by contamination with decomposition products despite a large number of studies on the synthesis and characterization of peroxide polymers.…”

Synthesis, spectral characterization, and thermochemical studies of poly(phenyl methacrylate peroxide)

“…Generally, vinyl polyperoxides have a low molecular weight 26 (M n ϭ 300 -5000) because of various chain transfer reactions occurring during oxygen copolymerization. A detailed examination of the mechanism of formation revealed that this category of polymers undergo facile degradation during polymerization, generating chain transfer agents such as aldehydes, which react with macro growing radicals, resulting in a low molecular weight.…”