Synthesis and Photopolymerization of Novel N-vinyl Amide Monomers and Synthesis and Characterization of a One-Component Maleimide Epoxy Resin

Date of Award


Degree Type


Degree Name

Doctor of Philosophy (PhD)


Polymers and High Performance Materials

First Advisor

Lon J. Mathias

Advisor Department

Polymers and High Performance Materials


In Part I, a series of novel N -vinyl amide monomers was synthesized and their photopolymerizations attempted. A series of N -alkyl or aromatic-N -vinyl formamide derivatives was synthesized. Their photopolymerization behavior was compared to that of three commercial N -vinyl amide monomers, N -vinyl formamide, N -vinylpyrrolidone, and N -vinycaprolactam. Of the synthesized derivatives, only N -benyl-N -vinyl formamide and t -butyl-α-(N -vinylformamido)methacrylate photopolymerized. The lack of polymerization in the remaining derivatives is attributed to steric hinderance due to the cis conformation of the vinyl moiety with respect to the amide bond. A crosslinker based on N -vinylpyrrolidone was also synthesized, and its photopolymerization behavior was investigated in both aqueous and bulk conditions. The kinetic behavior of this bis-N -vinylpyrrolidone crosslinker, as well as that of an analogous monofunctional N -vinylpyrrolidone monomer with a hexyl side chain was investigated. Both the crosslinker and the monomer showed substantially higher rates of polymerization than N -vinylpyrrolidone itself. This increase in rate was attributed to a decrease in termination events due to steric bulk of the monomer. In Part II, an adduct of N -(p -carboxyphenyl)maleimide and allyl glycidal ether was synthesized. The thermal curing behavior of this adduct was investigated by TGA, DTA, and DSC and compared to that of a commercial bismaleimide resin, Matrimid 5292(TM). A weight loss due to water loss upon etherification was seen by TGA, occurring at 205°C. A curing exotherm beginning at 200°C was seen by DTA and DSC. The cured polymer was dark red to brown and brittle. Initial attempts at carbon fiber composite formation were unsuccessful.