Synthesis and characterization of copolymers containing azlactone functionality

This thesis describes the synthesis and characterization of copolymers containing, 2-vinyl-4,4-dimethylazlactone (VDMA). VDMA has previously been shown to react readily with a variety of nucleophiles (e.g. amines), and incorporation of small amounts of VDMA into polymers of common use, (e.g. PMMA) leads to materials with characteristics of the parent material, and the added benefit of a reactive site within the copolymer for potential polymer modification.; There are three main avenues of research addressed in this thesis. First, the copolymerization of methyl methacrylate (MMA) or N,N-dimethylacrylamide (DMA) with VDMA was examined for the specific purpose of measuring monomer reactivity ratios. Copolymerizations were performed using free-radical techniques, and monitored by gas-chromatography as a function of monomer consumed. Copolymer composition was extracted from 1H-NMR, and linear and non-linear methods were used to determine monomer reactivity ratios.; Second, polymeric microspheres of methyl methacrylate (PMMA) were prepared via emulsion polymerization using potassium persulfate (KPS) as initiator. In the emulsion procedure VDMA was added to the preparation in varied weight percent. FT-IR analysis indicated the hydrolysis of VDMA to give N-acryloylmethylalanine, (NAMA), in addition to copolymerization of VDMA into the particles in the early stages of the emulsion polymerization. The subsequent hydrolysis of VDMA in the copolymer produced carboxyl functionality that served to stabilize the microspheres and had a significant effect on particle size, particle size distribution, and morphology, but little effect on molecular weight or thermal properties. In addition, the effect of varied initiator concentration [KPS] showed little effect on particle size and size distribution, or on molecular weight or thermal properties of polymer particles.; Third, a novel carbohydrate containing monomer was prepared by reacting VDMA with 1,2;5,6-diisopropylidene-alpha-D-glucofuranose (DAG) in chloroform solution. The resulting monomer was easily homopolymerized as well as copolymerized with methyl methacrylate (MMA) to give high molecular weight polymers. Upon removal of the isopropylidene groups from the polymer, water contact angles decreased for polymeric films, indicating a more hydrophilic surface. The addition of a carbohydrate moiety to MMA copolymers increases its hydrophilicity and allows for use of the new polymer as a biomaterial in a potentially wide variety of applications.