The Synthesis Of Chiral Polymerizable Monomers And Research On Their Polymerization

The chiral polymer is a new kind of functional polymer which can be applied in many fields, such as medical sanitation, biochemistry, agriculture chemical production, material science,asymmetric synthesis and asymmetric catalysis ,etc..Nine kinds of new chiral unsaturated esters were synthesized through the condensation of methyl-S-(-)-lactate, S-(-)-α-phenylethyl alcohol and (S)-(+)-2-butanol, with acrylic acid, methacrylic acid and 10-undecylenic acid under the catalytic of N,N'-dicyclohexyl carbodimide(DCC) and 4-(N,N-dimethylamino)pyridine (DMAP).And three chiral unsaturated esters were synthesized through the condensation of N-Boc-L-alanine, N-Boc-L-phenylalanine, N-Boc-L-isoleucine with allyl alcohol under the same catalysts mentioned above.Five kinds of chiral unsaturated amides were synthesized through the condensation of S-(-)-α-phenylethylamine, N-Boc-L-tryptophan,N-Boc-L-glutamine with unsaturated acyl chloride. Four kinds of new chiral unsaturated amides were synthesized by three steps using N-Boc-L-alanine, N-Boc-L-phenylalanine, N-Boc-L-isoleucineand as chiral resources.The first step was the condensation of the reagents mentioned above with butylamine under the catalytic of DCC and DMAP. The second was deprotection.The third was the condensation with unsaturated acyl chloride.The process of synthesis and proportion were determined.The mechanism of the reaction was discussed. The products were characterized by the infrared spectrum, nuclear magnetic resonance and organic ultimate analysis.Several kinds of polymerizable monomers synthesized above were homopolymerized or copolymerized with styrene or methyl methacrylate. The polymers were characterized by the infrared spectrum,nuclear magnetic resonance and differential scanning calorimetry. The polymers will be used as reagents for chiral resolution and stationary phase of Capillary Electrophoresis.At last, the crosslinking polymer microsphers, with different side chiral groups, were synthesized by two methods,ie,suspension polymerization and seeding emulsion polymerization. The effects to the particle diameter and the dispersion degree of the microspheres were discussed. The polymer microspheres will be used as stationary phase of High Performance Liquid Chromatography.