The Synthesis Of Polysiloxane Chiral Stationary Phase

The chiral polymer is a new kind of functional polymer , because of the existence of the chiral carbon or the asymmetric factor,the chiral polymer has many excellent and special performance in many aspects.The chiral polymer are used as stationary phase of liquid chromatography,which can be applied to many fields,such as medical sanitation,biochemistry,agriculture chemicals,material science,asymmetric synthesis and asymmetric catalysis,etc.Three kinds of chiral amides,which coulde be used to addition polymerization,were synthesized using condensation of S-(-)-α-phenylethylamine with acryloyl chloride,methylacryloyl chloride,and 10-undecylenoyl chloride.The best process of synthesis and proportion were determined.And the productions were purified through recrystallization method. And then the productions were characterized by the infrared spectrum analysis,NMR and organic ultimate analysis and the reaction mechanism was discussed also.Nine kinds of new chiral unsaturated esters were synthesized using methyl-S-(-)-lactate,S-(-)-α-phenylethyl alcohol, and (S)-(+)-2-butanol as chiral pool under the catalytic of N,N'-dicyclohexyl carbodimide(DCC) and 4-dimethyl aminopyridines.The mechanism of the reaction was discussed respectively.The productions were characterized by the infrared spectrum analysis,NMR and organic ultimate analysis.The result of specific rotation indicated that the optical rotation of the products was not changed except the derivative of 2-butanol.But the ability of specific rotation has changed.The polysiloxanes,which have differential molecular weight and hydrogen content, were synthesized by two ways,ie, telomerization of octamethyltetrasiloxane and polyhydromethylsiloxane and copolymersation of monomers.The chiral monomers prepared above were grafted to the two kinds of the polysiloxane respectively through the hydrosilylation addition reaction.The chain structure of the products were characterized through the infrared spectrum analysis.According to the contrast of specific rotation determination,we confirmed that the optical rotation of the grafting polysiloxane were not changed,but the ability of optical rotation was changed.Then the chiral polymers which will be used in the chiral resolution were synthesized through the homopolymerizing of 10-undecylenic acid(α-methoxylcarbonyl)ethyl ester and the copolymerizing with methyl methacrylate.Chiral technical was established on the scientific foundation. At present the research of chiral polymers is also restricted in the laboratory synthesis stage, although the amazing result is obtained,its research work is just began. Especially more efforts in the synthesis mechanism were needed,and the structure relations, as well as chiral polymer application, still need to be further researched.