Piperazin N-N'- metilenbisakrilamid ve alkil aminler kullanarak suda çözünebilen kopolimerlerin sentezi

Abstract

Bu çalışmada N,N-Metilenbisakrilamid ile piperazinin oluşturduğu kopolimere üçüncü komponent olarak farklı alkil aminler eklenip elde edilen polimerlerin özellikleri belirlenmiştir. Kopolimerdeki piperazin miktarı azaltılıp yerine oktilamin ve dodesilamin eklenmiştir. Polimerlerdeki oranlan MBA % 50, piperazin % 40 ve alkilamin % 10 olarak alındı. Alkilamin katılarak elde edilen kopolimerin suda çözünürlükleri incelendiğinde oktüaminle oluşturulan kopolimer suda çözünürken, dodesüaminin hidrofob karakteri onun çözünmesini engelledi. Elde edilen polimerlerin özellikleri viskozimetrik, İR ve UV ölçülmeliyle belirlendi. Bu polimerlerin Cu2+ ile oluşturdukları kompleksler elde edildi. Ortama BSA (Bovine Serum Albumin) proteini katarak üçlü kampleks oluşumu incelendi.

Since the usage of polymers in medicine at recent time, polymers that are dissolved in water and degredated in living organisms are required to be synthesized. For this reason, the synthesis of polymers that contain the physiological active groups in their structure and examining them are very important. Water soluble systems (polymers, policomplexes and other polymer madificontions) are used as a physiological active substance at recent years. Application of some physico-chemical methods to these systems gives information about their structure. The synthetic polymers that contain nitrogen atoms in its structure have been used in medicine and biological sciences. As an example, effects of synthetic poliymers are; the adjuvant effect (secondary chemical substances that enter to the organism to increase the immunity of organism with antigens), dissolving of sediments that prevent circulation of blood, antimicrobial effect, prolongation effect (protection of active substances of medicine for a long time in an organism), drug delivery system (gradual releasing of medicine in an organism) etc. There must be two different structure of polymers in order to achieve above purposes, 1) Polymer must be resistant to enzymatic degradation to stay for a long time in the organism. For this reason, polymers must be combined with C-C sigma bonds. 2) There must be biodegradable bonds (C-N, C-S, C-P, C-O) in the structure of the polymers to stay in an organism for a short time. The objective of this study is to synthesize polymers that are biodegradable in the organism. In other words the new kind of physiological active polymers that contain C-N bonds in its structure will be synthysized and physico-chemical properties will be investigated. In this study, by the introduction of primary alkyl amines ( number of C > 8, more hydrophobic character) three components copolymers are synthesized and their structures are investigated in ER, UV and viscozimetric measurements, Piperazine-methylenebisacrylamide copolymer was obtained by using equal mole of each monomer. 2,1325 g N,N -methylenebisacrylamide and 1,19 g piperazine were mixed with 7 ml water. Polymerization was carried out under nitrogen atmosphere at 50°C. Properties at this copolymer have been investigated by using viscozimetric and IR measurements. The resulting polymer is water soluble. Polymerization occurs by migration of active H atoms of piperazine to double bond of methylenebisacrylamide. This bond is broken down and monomers are bound to each other. VI CH2=CH-C0-NH-CH2-NH~C0-CH=CH2 + Hf( ^IH ' * -. MN VlH HN N-CH2-CH2-C0-NH-CH2-NH-C0-CH =CH2 MN NH + CH2 = CH-CO-NH-CH2-CO-CH=CH2 - ^l-CH2CH2C0NHCH2NHC0(CH2J2-N N-CH2CH2C0NHCH2NHC0(CH2)2-^-l Addition of amine groups to above system that contain active hydrogen atom causes reaction between amine hydrogen with double bond of methylenebisacrylamide at the same time with piperazine. Thus, piperazine and other amine reacts with methylenebisacrylamide by means of competative reaction. On the basis of this knowladge, two kinds of primary amines (octyl and dodecyl) are introduced to the mixture of methylenbisacrylamide and piperazine. Selection of these amines is based on their higher number of C atoms. So, the amines that contain different C atoms have different hydrophobic effect. The monomer ratio of MBA / Piperazine is 1/1 at the above polymerization reaction. When octylamine and dodecylamine were introduced into polymerization, mole ratio of MBA is kept constant at 50%, piperazine is at 40% and alkylamine is at 10%. Polymerization was done at the same conditions by adding octylamine and dodecylamine. Polymerization reaction could be repesented schematically as follows. vn CM X en X LJ I C-- CM LJ I CM X + CM X I o LJ r X CM en X LJ I CM X LJ I O LJ I X.z. I CM I O CM I O LJ 1 CM LJ I I O LJ I X LJ II CM X LJ CM X o LJ CM "cm I CM CM LJ O LJ CM X LJ CM X LJ I "CM ? r» ""cm CO X X LJ LJ \- CM "?» X LJ O LJ CM X CM CM X LJ O LJ CM X LJ X z o LJ CM X LJ CM I X LJ II CM X LJ O LJ X LJ II CM vm Ol X ı_J II X LJ O CM X LJ m X LJ I CM X LJ I CM X + X /2s co + CM LJ II X LJ I O LJ I X ı CM X LJ I I O LJ I X LJ II CM X LJ CM 1-5- CM I CM X LJ I O LJ I X ı CM o X LJ O LJ X CN I O LJ I CM X LJ I CM II X LJ I O LJ I CM X LJ I X ı O LJ II CM CM "cm I CM *CM O LJ /2\ I CM "cm O LJ X CM X LJ X LJ II CM O LJ CM X LJ CM X LJ I /A IX FT -IR results of obtained copolymers and their monomers were taken. Polymerization of alkyl amines was carried out by using water and water + alcohol mixture. Changing initial conditions has no effect on polymerization. This was understood by examining copolymers with IR and viscozimetric measurements. IR spectrum of different copolymes are similar to each other and nsp/c values for different copolymers were very near to each other. Because of higher hydrophobic character of dodecyl amine, three component copolymer of dodecyl amine is not water soluble so only IR results were obtained. Cu2+ ion was introduced into polymer solution. Our polymer contains N and O atoms which have lone pairs of electrons on their valance shell. These lone pairs form coordination bond between Cu2+. Because of this interaction, polymer - Cu2+ complex was formed and precipitated with time. Bovine Serum Albumin (BSA) protein was introduced in to the rections of Cu2+ and copolymer. BSA also contains - COOH and - NH2 groups so it easily makes coordination bonds with Cu2+.Polymer-protein -Cu2+ complexes were obtained.