Ek_A1. : İstanbul Teknik Üniversitesi. Tez Türü ve Tarihi : Doktora Mart 2010 ÖZET FARKLI TOPOLOJİLERE SAHİP BAROPLASTİKLER.

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1 Ek_A1 Üniversitesi : İstanbul Teknik Üniversitesi Enstitüsü : Fen Bilimleri Anabilim Dalı : Polymer Science and Technology Programı : Polymer Science and Technology Tez Danışmanı : Prof. Dr. Metin H. ACAR Tez Türü ve Tarihi : Doktora Mart 2010 ÖZET FARKLI TOPOLOJİLERE SAHİP BAROPLASTİKLER Şebnem İNCEOĞLU Bu çalışmanın esas amacı olarak, farklı topoloji ve segmentlere sahip olan polimerlerin yapısının reolojik akışa etkisini incelemek amacıyla, varolan baroplastik malzemelerin genişletilmesi hedeflenmiş ve yeni tür baroplastik malzemeler için topoloji, kompozisyon, molekül ağırlığı, geri dönüşüm çevrimi ve basıncın etkisi araştırılmıştır. Öncelikle çok fonksiyonlu başlatıcılar ve bu başlatıcılar kullanılarak değişik topolojilerde homopolimerler ve bu homopolimerden yola çıkılarak farklı topolojilerde ve molekül ağırlıklarında iyi tanımlanmış blok kopolimerler atom transfer radikal polimerizasyonu ile sentezlenmiştir. Elde edilen blok kopolimerlere oda sıcaklığında basit sıkıştırma ve/veya ekstrüzyon işlemleri uygulanarak baroplastik özellikleri incelenmiştir. Bunlara ek olarak, oda sıcaklığında basınç altında proses edilebilen baroplastik malzemelerin proses sonrasındaki fiziksel değişimleri (düzenli halden düzensiz hale geçişi) termal, morfolojik, reolojik ve mekanik özellikleri açısından incelenmiştir. Ayrıca, baroplastikler proses yardımcı maddesi olarak değerlendirilerek, yaygın kullanımı olan ve yüksek sıcaklıklarda proses edilen ticari polimerler ile fiziksel karıştırılarak bu polimerlerin de oda sıcaklığında ilk kez proses edilebilirlikleri gösterilmiştir. Tez çalışmasında, birçok kez tekrarlanan geri dönüştürülme işlemlerinde baroplastik malzemenin bozunmaya uğramadan ve madde kaybı olmadan %100 geri kazanım sağlandığı gözlemlenmiştir. Bu sonuç baroplastik malzemelerin sonsuz kez geri dönüştürülerek kullanılabileceği şeklinde değerlendirilebilir. Bu çalışmada, yüksek ve düşük sıcaklıkta proses koşulları karşılaştırıldığında, oda sıcaklığında proses işleminin yüksek basınçlar gerektirmediğinden dolayı endüstride termal prosesler için kullanılan cihazların baroplastik malzemeler için de kullanılabileceği değerlendirilmesi yapılabilir. Tüm bu sonuçlar göz önüne alındığında kaynak kullanımı azaltılabileceğinden farklı topolojilere sahip baroplastikler, ekonomiye katkı sağlayan ve çevre dostu yeni malzemeler olarak değerlendirilebilir. Anahtar Kelimeler: Baroplastik, blok kopolimer, ATRP, faz ayrımı Bilim Dalı Sayısal Kodu:

2 Ek_A2 University : İstanbul Technical University Institute : Institute of Science and Technology Science Programme : Polymer Science and Technology Programme : Polymer Science and Technology Supervisor : Prof. Dr. Metin H. ACAR Degree Awarded and Date : PhD March 2010 ABSTRACT DIFFERENT TOPOLOGIES ON BAROPLASTICS Şebnem İNCEOĞLU The main aim of this study is an attempt to understand, the effect of structure on rheological flow of polymers having different topologies with different segments. The goal of expanding the range of existing baroplastics has been achieved and the effect of topologies, compositions, molecular weights, recycling cycles and pressure were examined in depth for obtained novel baroplastic materials. First, in order to synthesize well defined block copolymers with different topologies and molecular weights, suitable multi functional initiators and from them well-defined homopolymers were synthesized via atom transfer radical polymerization. Obtained block copolymers baroplastic properties were investigated by simple compression and/or extrusion at room temperature. One additional step was taken and the physical changes (from ordered to disordered state) of baroplastic materials after processing at room temperatures were included and in order to obtain understanding of the processability of resulting properties, morphological, thermal, rheological and mechanical property measurements were performed. Additionally, the possibility of using optimized amount of baroplastic materials as processing aid, in order to process high temperature processing polymers at room temperature under pressure, was demonstrated for the first time with polystyrene that is a commodity and high temperature processing polymer. During thesis work, it has been observed that baroplastic materials could be recovered 100% without any degradation after multiple recycling cycles. From this result, it can be concluded that the baroplastic materials may be recycled for infinity times. Herein, when high and low temperature processing were compared, the equipments that are used for the manufacturing of current commercial plastics could be suitable for baroplastic processing as well, since the room temperature processing does not require high pressure. Thus, with all this reduced resource utilization, baroplastics can be considered as new environment-friendly materials with different topologies contributing to the economy. Keywords: Baroplastic, block copolymer, ATRP, phase separation Science Code:

3 BU TEZ ÇALIŞMASINDAN YAPILAN BİLİMSEL YAYINLAR THE SCIENTIFIC PUBLICATIONS EMANATING FROM THIS THESIS WORK Uluslararası Hakemli Dergilerde Yayınlanan Makale ve Kitap Bölümleri 1. Inceoglu, S., Acar, M. H., Novel Baroplastic Materials, Progress in Controlled/Living Radical Polymerization, ACS Symposium Series Book; Matyjaszewski, K., Ed, Philadelphia, PA, Materials Prepared by ATRP, Chapter 21, Acar, M. H., S. Inceoglu, Baroplastic in different topologies and used as compatibilizer, Abst. Paper Am. Chem. Soc. 236, 270, Polym. Preprint 49(2), Acar, M. H., Becer, C. R., Ondur, H. A., Inceoglu, S., Alkylated Linear Amine Ligands for Homogeneous Atom Transfer Radical Polymerization, In Controlled/ Living Radical Polymerization: From Synthesis to Materials, ACS Symposium Series Book; Matyjaszewski, K., Ed, Washington, DC, 994, Chapter Acar, M. H., Becer, C. R., Ondur, H. A., Inceoglu, S., Synthesis of alkylated linear amine ligands and their effect on homogeneous ATRP, Abst. Paper Am. Chem. Soc. 230, 242, Polym. Preprint, 46(2), Inceoglu, S., Olugebefola, S. C. Acar, M. H., Mayes, A. M., Atom Transfer Radical Polymerization using poly(vinylidene fluoride) as macroinitiator, Designed Monomers and Polymers, 7, Inceoglu, S., Tunca, U., Hızal, G Synthesis of styrene-methyl methacrylate graft and graft-block copolymers via combination of ATRP and SFRP, Designed Monomers and Polymers, 7, 203. Bildiri listesi Uluslararası Hakemli Sempozyumlar 1. Inceoglu, S., Acar, M. H., Plastics Processing: Energy saving without heating, 11 th Pasific Polymer conference, PPC11, Cairns, Avustralya, 6-10 December, oral 2. Inceoglu, S., Acar, M. H., Decreasement of nanophase separation on plastics International Conference on Nanomaterials and Nanosystems, NanoMats, ITU, Istanbul, Turkey, August, oral presentation (2 nd placed award). 3. Acar, M. H., Inceoglu, S., Baroplastics in different topologies and their compatibilizer, Controlled/Living Radical Polymerization, at the National Meeting of the American Chemical Society in Philadelphia, PA, USA (17-21 August), invited speaker, oral

4 4. Inceoglu, S., Acar, M. H., Baroplastic Elastomer: In Different Topologies and used as Compatibilizer, New Smart Materials via Metal Mediated Macromolecular Engineering: From Complex to Nano Structures, NATO Advanced Study Institute (ASI), (1-12 September) poster presentation (3 rd placed award). 5. Acar, M. H., Inceoglu, S., Baroplastic elastomers, New Smart Materials via Metal Mediated Macromolecular Engineering: From Complex to Nano Structures, NATO Advanced Study Institute (ASI), Antalya, Turkey, (1-12 September 2008) oral 6. Inceoglu, S., Acar, M. H., Baroplastic Elastomer: In Different Topologies and used as Compatibilizer, The Polymer Processing Society 24th Annual Meeting, PPS24, Salerno, Italy, (15-19 June) oral 7. Acar, M. H., Inceoglu, S., Baroplastics in different topologies and their compatibilizer, National Meeting of the American Chemical Society in Controlled/Living Radical Polymerization, ACS, Washington, USA (17-21 August), invited speaker, oral 8. Inceoglu, S., Acar, M. H., Baroplastics in Different Topologies and Used as Compatibilizer, Controlled/Living Polymerization: From synthesis to applications, CLP07, Antalya, Turkey, (25-29 October) oral presentation (1 st placed award). 9. Saner, B., Birkan, B., Menceloglu, Y. Z., Synthesis of PVDF-based copolymers, Controlled/Living Polymerization: From synthesis to applications, CLP07, Antalya, Turkey, (25-29 October) poster 10. Bozok, N., Inceoglu, S., Acar, M. H., The effect of stirring rate on heterogeneous ATRP, Controlled/Living Polymerization: From synthesis to applications, CLP07, Antalya, Turkey, (25-29 October) poster 11. Zorvaryan, A., Inceoglu, S., Acar, M. H., Alkylated polyethyleneimine ligand for homogeneous atom transfer radical polymerization, Controlled/Living Polymerization: From synthesis to applications, CLP07, Antalya, Turkey, (25-29 October) poster 12. Inceoglu, S., Acar, M. H., Different topologies on baroplastic elastomers 1st European Chemistry Congress, EuChems06, Budapest, Hungary, (27-31 August) poster 13. Acar, M. H., Becer, C. R., Ondur, H. A., Zorvaryan, A., Deniz, O., Bekmez, M., Bozok, N., Inceoglu, S., Atom transfer radical polymerization: homogeneous or heterogeneous? 1 st European Chemistry Congress, EuChems06, Budapest, Hungary, (27-31 August) oral 14. Zorvaryan, A., Inceoglu, S., Acar, M. H., Alkylated polyethyleneimine ligand (APEI) for homogeneous atom transfer radical polymerization 1 st European Chemistry Congress, EuChems06, Budapest, Hungary, (27-31 August) poster

5 15. Birkan, B., Inceoglu, S., Menceloglu, Y. Z., Acar, M. H., Design and synthesis of novel polymeric materials for proton exchange membrane fuel cell applications, 2005 International Hydrogen Energy Congress, (IHEC 2005), İstanbul, Turkey (13-15 July), oral 16. Acar, M. H., Becer, C. R., Ondur, H. A., Inceoglu, S., Synthesis of alkylated linear amine ligands and their effect on homogeneous ATRP, Fall National ACS meeting, Washington, D. C., ABD (27 August-1 September) oral 17. Inceoglu, S., Olugebefola, S. C., Acar, M. H., Mayes, A. M., Atom Transfer Radical Polymerization using PVDF as macroinitiator, 40 th IUPAC International Symposium on Macromolecules World Polymer Congress, Macro2004 (4-9 July) poster 18. Inceoglu, S., Tunca, U., Hızal, G., Synthesis of styrene-methyl methacrylate graft and graft-block copolymers via combination of ATRP and SFRP, The 5 th International Conference on Advanced Polymer via Macromolecules Engineering, APME5, (21-26 June) poster 19. S. Inceoglu,, M. H. Acar, A. M. Mayes, Alkyl Floride as an initiator in ATRP, The 5 th International Conference on Advanced Polymer via Macromolecules Engineering, APME5, (21-26 June) poster presentation (2 nd placed award). Ulusal hakemli sempozyumlar 1. Kocaturk, H., Inceoglu, S., Birkan, B., Celik, S. U., Bozkurt, A., Menceloglu, Y. Z., Acar, M. H., Synthesis and characterization of PVDF-based proton conductive copolymers, IV. National Hydrojen Energy Congress and Exhibition, UHK 2009, Kocaeli University, (15-16 October) oral 2. Inceoglu, S., Baroplastic: New approach for plastic processing, New Polymeric Materials and Technology Workshop, NPMT, Çanakkale, Turkey, Çanakkale 18 Mart University, (17-19 April), invited speaker, oral 3. Kocaturk, H., Inceoglu, S., Acar, M. H., PVDF based copolymers New Polymeric Materials and Technology Workshop, NPMT, Çanakkale, Turkey, Çanakkale 18 Mart University, (17-19 April) oral 4. Bilal, A. S., Inceoglu, S., Acar, M. H., Recycling and thermal characterization of baroplastic, New Polymeric Materials and Technology Workshop, NPMT, Çanakkale, Turkey, Çanakkale 18 Mart University, (17-19 April), oral 5. Catlı, C., Inceoglu, S., Acar, M. H., New synthetic approach for star and star- block (co)polymers, New Polymeric Materials and Technology Workshop,

6 NPMT, Çanakkale, Turkey, Çanakkale 18 Mart University, (17-19 April), oral 6. Buyukaslan, E., Inceoglu, S., Acar, M. H., Baroplastic as processing aid New Polymeric Materials and Technology Workshop, NPMT, Çanakkale, Turkey, Çanakkale 18 Mart University, (17-19 April), oral 7. Inceoglu, S., Acar, M. H., Baroplastic: Synthesis, characterization and application, Nanoscience and Nanotechnology Conference, NanoTR4, ITU, Istanbul, Turkey, (9-13 June) poster presentation (2 nd placed award). 8. Inceoglu, S., Homogeneous ATRP with alkylated linear amine ligands, 1st National Polymer Science and Technology Congress, ODTU, Ankara, Turkey (June) oral 9. Kösker, D., Inceoglu, S., Birkan, B., Menceloğlu, Y. Z., Acar, M. H., Design of new polymeric membranes for hydrogen fuel cells, 1st National Science and Technology Congress, ODTU, Ankara, Turkey (June) (2 nd placed award) poster 10. Zorvaryan, A., Inceoglu, S., Acar, M. H., Synthesis of ethylated polyethyleneimine ligand and using in homogeneous atom transfer radical polymerization, 1 st National Polymer Science and Technology Congress, ODTU, Ankara, Turkey (June) poster 11. Bekmez, M., Inceoglu, S., Acar, M. H., Synthesis of three dentate linear amine ligands and using in homogeneous atom transfer radical polymerization 1 st National Polymer Science and Technology Congress, ODTU, Ankara, Turkey (June 2006) poster 12. Bozok, N., Inceoglu, S., Acar, M. H., Effect of stirring rate in heterogeneous atom transfer radical polymerization, 1 st National Science and Technology Congress, ODTU, Ankara, Turkey (June) poster 13. Deniz, O., Inceoglu, S., Acar, M. H., Synthesis of tetra dentate linear amine ligands and using in homogeneous atom transfer radical polymerization, 1 st Polymer National Science and Technology Congress, ODTU, Ankara, Turkey (June) poster