Pyrolysis of random and block copolymers of ethyl acrylate and methyl methacrylate

Pyrolysis gas chromatography can distinguish random from block copolymers of ethylacrylate and methyl methacrylate. The pyrograms depend on the pyrolytic temperature, the ratio of copolymerized monomers, the degree of conversion, and the method of polymerization. Larger amounts of ethyl methacrylate and methyl acrylate are formed on pyrolysis of random copolymers than of block copolymers. The presence of mixed dimers indicates random copolymerization. The sum of the percent recovery of ethyl alcohol and ethyl acrylate is fairly constant over a range of compositions and monomer sequence. Random copolymers produce less ethyl alcohol than ethyl acrylate on pyrolysis, while homopolymers and block copolymers produce more ethyl alcohol and less ethyl acrylate. In a set of random copolymers with different EA/MMA ratios, there is an increasing per cent recovery of EA monomer with decreasing EA in the copolymer, while ethyl alcohol shows the opposite behavior. The characteristic degradation patterns are thought to be governed by the availability of the tertiary hydrogen for ion by the alkoxy oxygen of a neighboring acrylate unit, the availability depending on the sequence distribution of acrylate/methacrylate molecules.