Akrolein bazlı kopolimerlerin sentezi ve modifikasyonları

Copolymerization of acrolein with N-vinylpyrrolidone (NVP) and its modification were aimed in this study. Polyacrolein is a polymer that its reactive aldehyde groups can easily be converted into oxime, amine, enamine, imine and bisulfite derivatives and has a potential on biological applications. There is very little information on poly (acrolein-co-vinylpyrolidone) in the literature.At the first stage, the free radical copolymerization of acrolein with N- vinylpyrrolidone (NVP) was carried out by using potassium persulfate (K2S2O8), as an initiator in water at 65 oC. The conversion of monomer mixtures in different mole ratios (58/42, 62/38 and 74/26) to polymers was studied in various time periods.The conversions of monomer mixtures to polymer were obtained in 192h as 23 %, 19% and 31% respectively.At the second stage, the monomer reactivity ratios were determined by using Fineman Ross (FR), Kelen Tüdos (KT), Extended Kelen Tüdos (E-KT), Mayo Lewis (M-L), and PREVM methods. The copolymer compositions were determined using elemental analysis and FT-IR analysis data method. By using elemental analysis data r1= 0.44 and r2= -0.082 (FR), r1= 0.47 and r2= -0.065 (KT), r1= 0.46 and r2= -0.064 (E-KT), r1= 0.49 and r2= -0.065 (M-L), r1= 0.49 and r2= -0.049 (PREVM) were obtained. By using FT-IR analysis data r1= 0.36 and r2= -0.077 (FR), r1= 0.41 and r2= -0.031 (KT), r1= 0.41 and r2= -0.033 (E-KT), r1= 0.36 and r2= -0.0010 (M-L), r1= 0.46 and r2= 0.004 (PREVM) were obtained.At the third stage, the aldehyde groups of acrolein in acrolein/NVP copolymers having different compositions (A74/NVP26 A62/NVP38 and A58/NVP42) were modified with hydroxylamine and phenylhydrazine reactions. The degree of modifications of modified copolymers synthesized at different times (24, 72, 120 and 168 h) was calculated by using elemental analysis results.The maximum degree of modification of oxime derivative copolymers was obtained in 168 h as 35 %, 50% and 73% in increasing content of acrolein in copolymers. The maximum degree of modification of phenylhydrazone derivative copolymers was obtained in 168 h as 27%, 30% and 39% in increasing content of acrolein in copolymers.All copolymers and their derivatives were characterized by FT-IR and NMR (1H-NMR, 13C-NMR) spectroscopy. Thermal properties and thermal stabilities of copolymers and their derivative were investigated by using DSC and TGA techniques.Solubility of copolymers and their derivatives were tested in various polar and non-polar solvents. Copolymers and their derivatives were found to be insoluble in common organic solvents. Results indicated that the poly(acrolein-co-vinylpyrrolidone) copolymers could only dissolve efficiently in trichloroacetic acid at 180oC, and partly soluble in aprotic polar solvents, such as in DMF, DMSO and pyridine around 180 oC. Furthermore their modification did not considerably affect the solubility behavior of copolymers.