Radicals continued structure

Methylpropene can be made to continue the process to yield high polymers—cationic polymerisation—but most simple alkenes will go no further than di- or tri-meric structures. The main alkene monomers used on the large scale are 2-methyIpropene (— butyl rubber ), and vinyl ethers, ROCH=CH2 (— adhesives). Cationic polymerisation is often initiated by Lewis acid catalysts, e.g. BF3, plus a source of initial protons, the co-catalyst, e.g. traces of HzO etc. polymerisation occurs readily at low temperatures and is usually very rapid. Many more alkenes are polymerised by a radical induced pathway, however (p. 320). 

The superoxide ion is a very weak hydrogen atom abstractor, which cannot continue the chain, and is destroyed via disproportionation with any peroxyl radical. So, the studies of the mechanisms of cyclic chain termination in oxidation processes demonstrate that they, on the one hand, are extremely diverse and, on the other, that they are highly structurally selective. The 20 currently known mechanisms are presented in Table 16.6. 

It is fortunate that in many cases we are able to show that there are stable substances (radicals, ions, etc.) of the same type as the hypothetical intermediate and that these more stable or more accessible substances actually have the chemical properties required of the hypothetical ones. Observable radicals and ions have a great variety of degrees of stability, depending on their structures. The extrapolation to the properties of the hypothetical intermediate is therefore a continuous one. 

The formation of silyl radicals in the exhaustive photolysis of the silane polymers was indicated by the isolation of disilanes of general structure (HSiRR SiRR H) as shown in Table 1. These materials accumulate in the photolysate and are photostable as they absorb only weakly at the irradiation wavelength (254 nm). Longer chain silanes are presumably continuously degraded under the conditions of the exhaustive irradiation. 

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