Ozonolysis of tetramethyl ethene, trans-4-octene or 1-octene in water leads to species, which after thermolysis at 60°C, generate radicals that initiate radical emulsion polymerization of methyl methacrylate (MMA). The course of the reaction is dependent on the structure of the alkene used. Tetramethyl ethene ozonates give the highest final yield of polymer, although the rates of polymerization observed from 0 to approximately 60% conversion are found to be essentially equivalent, regardless of the structure of the alkene employed. The difference in final conversion is attributed to changes in the half life of the generated peroxy species as a function of alkene structure. From these differences it is inferred that the initiating species are organo peroxides, probably hydroxy hydroperoxides, rather than hydrogen peroxide. Two latex systems, one stabilized by a cationic surfactant and the other by an anionic surfactant, were successfully prepared. Ozonolysis of water followed by heating in the presence of MMA does not produce polymer. However, ozonolysis of an aqueous sulphonate surfactant solution does produce a species that forms radicals on thermolysis and these radicals initiate radical polymerization of MMA, which proceeds to high conversion in emulsion.

Radicals, derived from the ozonates of alkenes, have been shown to be capable of initiating polymerisations of methyl methacrylate, styrene and vinyl acetate: in the case of styrene polymerisations the molar masses obtained at low conversion did not follow the expected trend with temperature.

Polyisobutylene (PIB) possessing alkene end groups was ozonized. NMR spectroscopy showed that trioxolanes and tetroxolanes were the main products and that these products were relatively stable. Thermolysis of the ozonolysis products generated radicals, which were shown by ESR spin-trapping experiments to be alkyl and oxyalkyl species. Thermolysis in butyl propionate solution also generated radicals with structures consistent with those expected of species arising from hydrogen abstraction from solvent. Thermolysis in the presence of methyl methacrylate (MMA) or styrene (S) led to polymerization of both. Size exclusion chromatography (SEC) and gradient polymer elution chromatography (GPEC) were used to investigate the possibility that the newly formed polymer might be attached to PIB. In the case of MMA polymerizations, the final product was a blend of the two homopolymers: no evidence for block copolymers could be seen by SEC or GPEC. In contrast, both SEC and GPEC indicated that a large fraction of the newly formed polystyrene was attached to PIB, most probably in the form of P(IB-b-S) block copolymer.

It is confirmed that the major products of ozonolysis of tetramethylethene (TME) in butyl acetate at temperatures between −60 and 20°C are the cyclic peroxides, acetone diperoxide and acetone triperoxide plus, at low temperatures, species which may be open-chain oligoperoxides. Solutions of ozonized TME are able to initiate polymerizations of methyl methacrylate at temperatures above 60°C. ESR spectroscopy has shown that acetone diperoxide does not generate significant concentrations of radicals below 140°C, so that the chief initiating species below this temperature must be acetone triperoxide and the oligoperoxides. Despite the fact that these species have different structures, indicated by their differing retention times in GC and also their different mass spectra, they behave kinetically as one species, i.e. conversions to polymer after polymerization times of 1h in the presence of ozonized TME are identical regardless of ozonolysis temperature.

Thermolysis of cyclic diperoxides gave radicals. When solution polymerization of MMA was initiated by acetone cyclic diperoxide transfer to solvent was the dominant feature of the initiation process. However, transfer in the bulk polymerization of MMA was not a significant feature. Initiation of polymerization of MMA in solution by dibenzyl ketone cyclic diperoxide occurred at lower temperatures, and also aromatic end groups, derived from initiation by benzyl radicals, could be detected by 1H NMR.