: İstanbul Teknik Üniversitesi. Tez Türü ve Tarihi : Doktora Eylül 2009 ÖZET

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1 Üniversitesi : İstanbul Teknik Üniversitesi Enstitüsü : Fen Bilimleri Anabilim Dalı : Kimya Programı : Kimyagerlik Tez Danışmanı : Prof. Dr. Yusuf YAĞCI Tez Türü ve Tarihi : Doktora Eylül 2009 ÖZET KONTROLLÜ POLİMERİZASYON VE KENETLENME PROSESLERİ İLE REAKTİF ARA BİLEŞİKLER VE MAKROMOLEKÜLLER SENTEZİ VE KARAKTERİZASYONU Demet Göen ÇOLAK Bu çalışma, zincir-ortası ve zincir-sonu fonksiyonel telechelic polimerler, makromonomer sentezi ve karakterizasyonu ile bunların çözünebilir ve işlenebilir tarak-tipi konjuge polimerlerin, örneğin poli(fenilen vinilen) (PPV) türevleri, hazırlanmasındaki kullanımını ele almaktadır. Zincir-ortası veya zincir-sonu dibromobenzen grupları içeren iyi-tanımlı, polistiren (PSt) veya poli(ε-kaprolakton) (PCL) esaslı polimerler atom transfer radikal polimerizasyonu (ATRP) veya halka açılma polimerizasyonu (ROP) gibi kontrollü polimerizasyon yöntemleri ile sentezlenmiştir. Bu polimerlerin amino- veya aldehitfonksiyonlu mono boronik asitler ile Suzuki tipi kenetlenme reaksiyonları, hedeflenen telechelic polimerlerin eldesini sağlamıştır. Daha ileri fonksiyonlandırmalar, azometin bağları oluşturmak üzere bu polimerlerin küçük molekül ağırlıklı uygun aldehit veya aminler ile kondenzasyonları sonucu gerçekleştirilmiştir. Sonuç olarak, zincir-ortası veya zincir-sonu amin-, aldehit-, pirol-, naftil- ve hidroksi-fonksiyonel telechelic polimerler elde edilmiştir. Bu fonksiyonel polimerler, farklı özellikler gösteren çeşitli moleküler yapıların hazırlanmasında makromonomerler olarak kullanılabilirler. İyi-tanımlı PCL veya PSt yan zincirli PPV türevleri, dialdehit fonksiyonel makromonomerlerin bis-(trifenil fosfonyum) tuzlarıyla birlikte, potasyum tert-butoksit varlığında Wittig polikondenzasyonu ile sentezlenmiştir. Sentezlenen bu PPV ler, başlangıç makromonomerleri gibi, genel organik çözücülerde oda sıcaklığında çözünebilmektedirler. Elde edilen PPV ler mavi ışık yaymaktadır ve oldukça yüksek relatif ve mutlak fotolüminesans kuantum verimi göstermektedir. Sonuç olarak, mükemmel çözünürlükleri ve optik özellikleri, bu malzemelerin yüksek verimli ışık yayan diodların (LED) tasarımında ve birçok alandaki çeşitli uygulamalarda kullanımlarını desteklemektedir. Anahtar Kelimeler: Telechelic, Makromonomer, ATRP, ROP, PPV Bilim Dalı Sayısal Kodu:

2 University : İstanbul Technical University Institute : Institute of Science and Technology Science Programme : Chemistry Programme : Chemistry Supervisor : Prof. Dr. Yusuf YAĞCI Degree Awarded and Date : PhD September 2009 ABSTRACT SYNTHESIS AND CHARACTERIZATION OF REACTIVE INTERMEDIATES AND MACROMOLECULES BY CONTROLLED POLYMERIZATION AND COUPLING PROCESSES Demet Göen ÇOLAK This study describes the synthesis and characterization of mid- and end-chain functional telechelics, macromonomers and their use in preparing soluble and processable comblike conjugated polymers, such as poly(phenylene vinylene)s (PPVs). Well-defined polystyrene (PSt) or poly(ε-caprolactone) (PCL) based polymers containing mid- or end-chain dibromobenzene moieties were prepared by controlled polymerization methods, such as atom transfer radical polymerization (ATRP) or ring opening polymerization (ROP). The reaction of these polymers with amino- or aldehydefunctionalized monoboronic acids, in Suzuki type couplings, yielded the corresponding desired telechelics. Further functionalization was achieved by condensation reactions of these polymers with appropriate low molecular weight aldehydes or amines to form azomethine linkages. As a result, mid- or end-chain amino-, aldehyde-, pyrrolyl-, naphthyl- or hydroxy-functional telechelics were obtained. These telechelics may serve as useful macromonomers in the preparation of various macromolecular structures displaying distinct characteristics. PPV derivatives bearing well-defined PCL or PSt as lateral susbstituents were synthesized by following a Wittig polycondensation using dialdehyde functional telechelic macromonomers in combination with bis(triphenylphosphonium) salts in the presence of potassium tert- butoxide. The resulting colored PPVs are soluble in common organic solvents at room temperature just as the starting macromonomers. They emit blue and exhibit very high relative and absolute photoluminescence quantum yield. Thus, excellent solubility combined with the optical properties favours the use of these materials in the design of highly efficient light emitting-diodes (LEDs) and in many applications in various areas. Keywords: Telechelic, Macromonomer, ATRP, ROP, PPV Science Code:

3 BU TEZ ÇALIŞMASINDAN YAPILAN BİLİMSEL YAYINLAR THE SCIENTIFIC PUBLICATIONS EMANATING FROM THIS THESIS WORK Uluslararası Hakemli Dergilerde Yayınlanan Makaleler 1. Muftuoglu, A.E., Cianga, I., Colak, D. and Yagci, Y., 2004: Synthesis of A(2)B and A(2)B(2) type miktoarm star co-polymers by combination of ATRP or ROP with photoinduced radical polymerization, Designed Monomers and Polymers,7(6), Kiskan, B., Colak, D., Muftuoglu, A.E., Cianga, I. and Yagci, Y., 2005: Synthesis and characterization of thermally curable benzoxazine-functionalized polystyrene macromonomers, Macromolecular Rapid Communications, 26(10), Colak, D., Cianga, I., Muftuoglu, A.E. and Yagci, Y., 2006: Synthesis and characterization of mid- and end-chain functional telechelics by controlled polymerization methods and coupling processes. Journal of Polymer Science Part A- Polymer Chemistry, 44(2), Tarkuc, S., Sahin, E., Toppare, L., Colak, D., Cianga, I. and Yagci, Y., 2006: Synthesis, characterization and electrochromic properties of a conducting copolymer of pyrrole functionalized polystyrene with pyrrole. Polymer, 47(6), Kiskan, B., Gacal, B., Tasdelen, M.A., Colak, D. and Yagci, Y., 2006: Design and Synthesis of Thermally Curable Polymers with Benzoxazine Fuctionalities, Macromolecular Symposia, , Colak, D.G., Cianga, I., Yagci, Y., Cirpan, A. and Karasz, F.E., 2007: Novel poly(phenylene vinylenes) with well-defined poly(ε-caprolactone) or polystyrene as lateral substituents: Synthesis and characterization, Macromolecules, 40(15), Nur, Y., Colak, D.G., Cianga, I., Yagci, Y. and Hacaloglu, J., 2008: Pyrolysis of poly(phenylene vinylene)s with polycaprolactone side chains. Polymer Degradation and Stability, 93(5), Nur, Y., Colak, D.G., Cianga, I., Yagci, Y. and Hacaloglu, J., 2008: Direct Pyrolysis Mass Spectrometry Studies on Thermal Degradation Characteristics of Poly(phenylene vinylene) with Well-Defined PSt Side Chains, Journal of Thermal

4 Analysis and Calorimetry, 94(1), Colak, D.G., Egbe, D.A.M., Birckner, E., Yurteri, S., Cianga, I., Tekin, E., Schubert, U.S. and Yagci, Y., 2009: Photophysical properties of PPP and PPV derivatives bearing polystyrene or polycaprolactone as side groups, European Polymer Journal, 45, Nur, Y., Colak, D.G., Cianga, I., Yagci, Y. and Hacaloglu, J., 2009: High temperature pyrolysis of poly(phenylene vinylene)s with poly(ε-caprolactone) or polystyrene side chains, Journal of Thermal Analysis and Calorimetry, 98(2), Uluslararası Kitap Bölümleri 1. Colak, D.G., Cianga, I., Yurteri, S. and Yagci, Y., New Polymers with Optoelectronic Properties by Combination of ATRP, ROP and Coupling Processes, In: New Smart Materials via Metal Mediated Macromolecular Engineering (Eds E. Khosravi, Y. Yagci, Y. Savelyev) NATO Science for Peace and Security Series-A: Chemistry and Biology, Springer, Ch. 4, pp Uluslararası Kongrelerde Sunulan Bildiriler 1. Colak, D., Cianga, I., Muftuoglu, A.E. and Yagci, Y., Synthesis and Characterization of Mid- and End-Chain Functional Telechelics by Controlled Polymerization Methods and Coupling Processes, (poster), APME 2005 (Advanced Materials via Macrmolecular Engineering), August 15-18, Istanbul, Turkey. 2. Colak, D.G., Cianga, I., Yagci, Y., Cirpan, A. and Karasz, F.E., Novel poly(phenylene vinylene)s with well-defined macromolecular side chains, (oral presentation), APME 2007, December 16-20, Miami, FL, USA. 3. Colak, D.G., Cianga, I., Yurteri, S. and Yagci, Y., New Polymers with Optoelectronic Properties by Combination of ATRP, ROP and Coupling Processes, NATO Advanced Study Institute (NATO-ASI), September 1-12, Antalya-Turkey. 4. Colak, D.G., Egbe, D.A.M., Birckner, E., Yurteri, S., Cianga, I., Tekin, E., Schubert, U.S. and Yagci, Y., 2009: Photophysical properties of PPP and PPV derivatives bearing polystyrene or polycaprolactone as side groups, (poster), APME 2009, October 4-7, Dresden, Germany. Ulusal Hakemli Kongrelerde Sunulan Bildiriler 1. Colak, D., Cianga, I., Muftuoglu, A.E. and Yagci, Y., ATRP, ROP ve Kenetlenme Reaksiyonları ile Makromoleküller Sentezi, (poster), XIX. Ulusal Kimya Kongresi, 30 Eylül-4 Ekim, Kuşadası, İzmir.

5 2. Colak, D., Cianga, I. and Yagci, Y., Synthesis and Characterization of Poly(phenylene Vinylene)s with poly(є-caprolactone) side Chains, (poster), XX. Ulusal Kimya Kongresi, 4-8 Eylül, Kayseri. 3. Colak, D.G., Cianga, I., Yagci, Y., Cirpan, A. and Karasz, F.E, Poli(εkaprolakton) veya polistiren yan zincirli poli(fenilen vinilen) sentezi ve karakterizasyonu, (poster), XXI. Ulusal Kimya Kongresi, Ağustos, Malatya.