Synthesis And Ring-opening Polymerization Of Functional Morpholines Dione And Anhydrides

Intelligent polymers which were named stimuli-responsive polymers werepolymers of a kind of stimulation to the external environment (solvent, reactant,temperature, pH, ions, electric field, light, stress and magnetic field, etc.), and certainphysical or chemical properties such as phase, shape, optics, mechanics, electricfield, surface energy, reaction speed, penetration rate which were able to chang.Temperature-responsive polymer could be easily used to the biomaterials such asdrug delivery systems in all kinds of environmental responsive materials. However,the application of polymers to drug delivery systems was difficult because moststimuli-responsive polymers (such as PNIPAM) were not biodegradable. Poly (esteramide)was widely used in drug carrier material, chemical and biological sensors,artificial skin, bone fixation, surgical suture materials, tissue repairmaterials,etc.because of its biodegrable and biocompatible properties. If a polymerwhich was designed, contained biodegradability, stimuli-responsive andbiocompatibility, it can be suitable for application of new polymer materials in thebody.In this thesis, firstly3-(N-alkyl) asparagine was synthesized by esterificationand aminolysis, secondly3-(N-alkyl acetamides)-6-methyl-2,5-morpholine dioneand homologue were synthesized by3-(N-alkyl) asparagine reacting withhalogenacylhalide and using L-aspartic as row material. The structure ofintermediates and products were characterized by NMR (1H NMR,13C NMR) andFourier-transform infrared (IR) spectra. Relative molecular mass were massspectroscopy (MS). In addition, products were characterized by elemental analysis.The main influencing factors of the monomer production rate were analyzed in detail.The synthesis conditions of monomer were optimized. Polymer of3-(N-alkylacetamides)-6-methyl-2,5-morpholine dione and homologue were synthesized byring-opening of monomers. The structure of product was characterized by NMRspectroscopy (1H NMR,13C NMR) and GPC. All the test results showed that theywere the tatget product. The results of the characterization of the polymer show thatthe catalyst has good catalytic activity and temperature-responsive and is able to gethigh molecular weight polymer. Its response temperature varies with substituents. The response temperature of Poly(3-(N-propyl acetamides)-6-methyl-2,5-morpholine dione) is34oC. The response temperature of Poly(3-(N-isopropylacetamides)-6-methyl-2,5-morpholine dione) is30oC. The response temperature ofPoly(3-(N-isobutyl acetamides)-6-methyl-2,5-morpholine dione) is15oC.In this thesis,3-(propionyl butylamine)-6-methyl-2,5-morpholine dione wassynthesized by “protection-acylation-deprotection-cycling” and using L-lysinehydrochloride as row material in order to get temperature-responsive and degradablepolymer. The structure of intermediates and products were characterized by NMRspectroscopy (1H NMR,13C NMR) and Fourier-transform infrared (IR) spectra.Relative molecular mass were mass spectroscopy (MS). In addition, products werecharacterized by elemental analysis. The main influencing factors of the monomerproduction rate were analyzed in detail. The synthesis conditions of monomer wereoptimized. Polymer of3-(N-alkyl acetamides)-6-methyl-2,5-morpholine dione andhomologue were synthesized by ring-opening of monomers. The structure of productwas characterized by NMR spectroscopy (1H NMR,13C NMR) and GPC. All the testresults showed that they were the tatget product. The results of the characterizationof the polymer show that the catalyst has no good catalytic activity andtemperature-responsive and is unable to get high molecular weight polymer.