Synthesis and Polymerization of New Di-octadecyl Ester Derivatives of α-hydroxymethyl Acrylate: A Structure-property Correlation for their Copolymers with Methyl Methacrylate

Lon J. Mathias, University of Southern Mississippi

Originally published in Journal of Polymer Science, Part A: Polymer Chemistry, Volume 46, Issue 23, 1 December 2008, Pages 7785-7793

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New ether dimer (ED-Od) and diester (ODE) derivatives of α-hydroxymethylacrylate, each having two octadecyl side chains, were synthesized and (co)polymerized to evaluate the effects of differences in the structures of the monomers on final (co)polymer properties, particularly glass transition temperature. The free radical polymerizations of both monomers yielded high-molecular weight polymers. Cyclopolymer formation of ED-Od was confirmed by 13C NMR analysis and the cyclization efficiency (0.95 or greater) was found to be as high as the cyclization efficiencies of the cyclopolymerizations of ether dimers of various alkyl α- hydroxymethylacrylates synthesized previously. Copolymers of both ED-Od and ODE with methyl methacrylate (MMA) showed significant Tg decreases over PMMA due to octadecyl side groups causing "internal" plasticization. Comparison of the Tg's of the copolymers of octadecyl methacrylate, ED-Od and ODE with MMA revealed that the impacts of these monomers on depression of Tg's are identical. That is, the magnitude of decrease in T g's was quantitatively related to the number of the octadecyl side groups in the copolymers rather than their placement on the same or randomly incorporated repeat units. © 2008 Wiley Periodicals, Inc.