Polymerization shrinkage of methacrylate esters.

The polymerization shrinkage of a range of poly(n-alkyl methacrylates) in the range C1 to C16, some of their isomers and the polymers of cyclic and heterocyclic methacrylates have been measured using densitometry. The percentage volume shrinkage decreases with the size of the substituent side group. This proved to reflect the fact that the change in molar volume on polymerizing a methacrylate ester is reasonably constant at 22 cc/mol irrespective of the geometry of the substituent group. However, the glass transition temperature of the polymer depends very critically on the geometry of the side group. Hence one method for the development of low shrinkage glassy polymers is to investigate methacrylate esters of large molar volume, but with side group geometry that results in a high glass transition temperature. Polymerization shrinkage can be used to determine the degree of conversion of a polymer, using the value of 22 cc/mol as the change in molar volume.