Design And Synthesis Of Novel Optically Active Poly(meth)acrylamides And Their Properties

Novel monomers of L-1-acryloyl-N-phenyl pyrrolidine-2-amide （L-APPCA） andN-（2-hydroxy-1-phenylet-hyl）-methacrylamide （L-HPEMA） were designed and synthesizedin this thesis. Polymers with different microstructure were obtained by radical polymerization,and the effect of reaction conditions on the chiral separation ability and tacticity of PAPPCAwere studied. The chemical structure of monomer and polymer was characterized by protonnuclear magnetic resonance （¹H NMR） and carbon NMR (¹³C NMR). The thermal propertiesof immobilized chiral stationary phase （CSP） were studied by thermogravimetric analysis（TGA）. The optical activity of PAPPCA was studied by polarimeter and circular dichroism（CD）. The separation ability of chiral polymers as CSP was studied by high performanceliquid chromatography （HPLC）.Novel chiral monomer of L-APPCA was synthesized by two steps reaction and purifiedby recrystallization and column chromatography. The structure and purity of L-APPCA wasconfirmed by¹H NMR. The radical polymerization of L-APPCA was carried out under drynitrogen in different conditions, such as different monomer concentration, type of solvent andtype of Lewis acid. The effect of polymerization conditions on optical rotation and CD spectraof monomer and polymers, molecular weight and polydispersity index （PDI） of polymerswere tested. The results showed that the CD spectra and molecular weight of obtainedpolymers was slightly influenced by the addition of Lewis acids.The chiral separation ability of PAPPCA with different microstructure as CSP wasstudied, and the effect of test condition on the chiral separation ability of this novel CSP wasdiscussed. The concentration of monomer for polymerization was usually0.5mol/L. The bestratio of hexanes to isopropanol in mobile phase for HPLC was hexane/isopropanol equal to90/10（v/v）. Immobilized-type chiral stationary phases were synthesized by grafting ofPAPPCA to aminopropyl functionalized silica gel in the absence and presence of Lewis acids.The results showed that the CSPs made in the presence of Lewis acids had better chiralseparation ability. For the same CSP, the ingredient and polarity of mobile phase mightinfluence the separation efficiency.Novel methacrylamide monomer of L-HPEMA was synthesized by the reaction ofmethacryloyl chloride and L-phenylglycinol in basic condition. The effect of solvent, Lewisacid, concentration of monomer and reaction temperature on polymerization of L-HPEMA was studied by free radical polymerization. The results showed that the lower polarity ofsolvent for polymerization, the higher isotacticity of the polymers when same Lewis acid wasapplied. Polymers would have different tacticity in the presence of various Lewis acids whenL-HPEMA was polymerized in the same solvent. Among the Lewis acid applied, rare earthmetal sulfonates was more contributed to the promotion of isotacticity of PHPEMA than rareearth metal chloride. The results of optical rotation and CD spectra showed that the opticalactivity of polymers was relative to the stereoregularity of polymers。...