The photochemical telomerisation of methyl methacrylate

Senogles, Ernest (1959). The photochemical telomerisation of methyl methacrylate. University of Birmingham. Ph.D.

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Abstract

The photochemically initiated polymerisation-transfer reaction between bromotrichloromethane and methyl methacrylate has been studied. Under suitable conditions low polymers of methyl methacrylate can be produced, and quantitative element analysis or vapour phase chromatography can be used to determine their composition. Correlation of the latter with feed composition enables values of Mayo’s transfer constant (C) to be found for methyl methacrylate type radicals of different size. These values can be resolved into their component propagation and specific transfer rate constants by determining overall reaction rates, rates of initiation, and the lifetime of the appropriate sized radical. Dilatometry has been used to obtain these latter measurements, the techniques of radical scavenging and intermittent illumination being utilised to evaluate the initiation rate and the radical lifetime respectively.
It was found that in going from the trimeric radical to the tetrameric there is a pronounced increase in reactivity in the debromination reaction, though a subsequent drop occurs when the radical becomes still larger. Propagation and termination reactivities for the corresponding radicals are, however, independent of radical size. The results are discussed.

Type of Work:

Thesis (Doctorates > Ph.D.)

Award Type:

Doctorates > Ph.D.

Supervisor(s):