Perflorofenil fonksiyonlu asiklik dien metatez polimerinin modifikasyonları

ADMET polymerization is the process of obtaining α,ω-diene monomers which are produced by appropriate olefin metathesis catalysts. Generally, metathesis procatalyst is activated by the first reaction with the diene type monomer and metal alkylidene is formed. When the resulting metal alkiliden isreacted with another diene, a reformed dimer and methylidene type is produced in the environment.Metal methylidene acts as the real catalyst in this reaction. These reactions of the monomer or the polymer causes ethylene gas to be produced and it is disposed of by applying vacuum. Accordingly, due to the Le Chatelier's principle, this process shifts the reaction towards polymerization. In an ADMET polymerization concentration of the reaction environment has a key role in producing polymer chains. Polymerizations which take place in a diluted reaction environment causes the product to be mostly in oligomeric structure. This is due to the fact that the monomer -which has double bonds on each end- after gaining an oligomeric structure during growth stage, it reaches a level of flexibility where it attacks its own diene end in a diluted reaction environment and forms an oligomeric ring. Consequently, the monomer which is in the diluted environment chooses the ring closing metathesis(RCM) instead of the ADMET. In order to prevent this, it is more appropriate to make the polymerization as bulk instead of in a solvent. Active ester reactions are popular types of reactions which are used in peptide synthesis in organic chemistry. It is known that active esters such as thiophenylesters, activated methyl esters and nitrthiophenyl esters are used in various synthesis reactions.Their use in polymer chemistry has become widespread and due to their high performance in mild reaction conditions, they became an important choice for polymer reactions. A frequently used active ester which is on the side chain of a synthesized polymer such as perfluorophenyl, helps to produce another completely different behaving polymer with an easily made substitution reaction. Obtaining modified polymers which show differences in solubility compared to the synthesized main polymer with the help of these modifications, provides many opportunities in medical applications. Especially when it is not very easy to synthesize the polymers with desired properties, active ester reactions proves to be a solution for these problems. Under normal cimcumstances, it can be very difficult or even impossible to modify a polymer, whereas if active esters are used as protectivegroups, modifications can be made and afterwards active ester functionality can be transformed into amide form with a pimary amine. In this research, ADMET polymer which contains active ester was tested with different types of catalysts and solvent systems. Obtained results showed that, the G1 catalyst and bulk system are the best reaction conditions. Characterization of the synthesized polymer was made without using any solvent while using G1 catalyst. Next, by reacting the resulting polymer with different amines without any need for an extra base, the easy leaving group of perfluorophenoxy were substituted with the used amines. In the second phase of the research, the obtained ADMET polymer was reacted with a base containing triple bond and made ready for a possible "azide-alkyne click" reaction. Then, the polymer was reacted with polyethylene glycol and it was characterized. All characterization processes are made by usingGPC, 1H NMR, 13C NMR, 19F NMR, DSC and FT-IR.