Atrp Ve Nmp Yönetmleri İle Crown Eter Bağlantı Noktası İçeren Pmma-b-ps Kopolimerlerinin Sentezlenmesi

Abstract

Bu çalışmada, atom transfer radikal polimerizasyonu(ATRP) ve nitroksi ortamlı radikal polimerizasyonu(NMP) yöntemleri ile crown eter bağlantı noktası içeren Poly (methyl methacrylate)-b-polystyrene (PMMA-b-PS) kopolimeri hazırlandı. Bu amaç için, 6, 7, 9, 10, 12, 13, 15, 16 – octahydro - 5, 8, 11, 14, 17 -pentaoxa-benzocyclopentadecene-2-carboxylic acid 3-(2-bromo-2-methyl-propionyloxy)- 2 - methyl - 2 - [2 - phenyl - 2 - (2, 2, 6, 6 - tetramethyl-piperidin-1-yloxy)-ethoxycarbonyl]-propyl ester (11) sentezlendi ve Metil metakrilatın (MMA) atom transfer radikal polimerizasyonu CuCl ve pentamethyldiethylenetriamine (PMDETA) sayesinde 60 oC gerçekleştirildi. Yapılan kinetik çalışmada, polimerizasyonun 1.dereceden ve kontrollu olduğu gözlendi. Elde edilen PMMA makrobaşlatıcı olarak kullanılarak, Stirenin (NMP) polimerizasyonu 125 0C de gerçekletirildi. Böylece Crown eter içeren PMMA-b-PS kopolimeri sentezlendi. Bu kopolimerin K+ ile kompleksleşmeleri araştırıldı.

Poly (methyl methacrylate)-b-polystyrene (PMMA-b-PS) containing a benzo-15-crown-5 unit at the focal point was prepared by combination of atom transfer radical polymerization (ATRP) and nitroxide-mediated radical polymerization (NMP). For this purpose, 6, 7, 9, 10, 12, 13, 15, 16 – octahydro - 5, 8, 11, 14, 17 -pentaoxa-benzocyclopentadecene-2-carboxylic acid 3-(2-bromo-2-methyl-propionyloxy)- 2 - methyl - 2 - [2 - phenyl - 2 - (2, 2, 6, 6 - tetramethyl-piperidin-1-yloxy)-ethoxycarbonyl]-propyl ester (11) was synthesized and used as an initiator in ATRP of methyl methacrylate (MMA) in the presence of CuCl and pentamethyldiethylenetriamine (PMDETA) at 60 oC. A linear behavior was observed in both plots of ln([M]o/[M]) vs. time and Mn,GPC vs. conversion indicating that the polymerization proceeded in a controlled manner. Thus obtained PMMA precursor was used as a macroinitiator in NMP of styrene (St) at 125 oC in order to give well-defined PMMA-b-PS with crown ether. Potassium picrate (K+ picrate) complexation of 11 and the block copolymer was studied and the resulting structure was investigated.