Microtacticity of poly(methacrylic esters) obtained by radical polymerization

The microtacticity of polymethacrylates prepared by radical initiated polymerization of monomers with side groups of increasing bulkiness is determined by high resolution nuclear magnetic resonance of the corresponding poly(methyl methacrylates). The syndiotacticity decreases systematically from poly(methyl methacrylate) to poly(triethylmethyl methacrylate) in the series of the saturated polymers. The aromatic polymethacrylates have a lower syndiotacticity than the corresponding saturated polymers and poly(trityl methacrylate) is the extreme case. The microtacticity of the polymers is undoubtedly determined by the bulkiness and the polarisability of the ester group as well as by specific interaction between the aromatic rings.