Polioksanorbornen Ana Zincirinin Bromlanması Ve Atom Transfer Nitroksit Radikal Birleşmesi Reaksiyonu İle Fonksiyonlandırılması
Polioksanorbornen Ana Zincirinin Bromlanması Ve Atom Transfer Nitroksit Radikal Birleşmesi Reaksiyonu İle Fonksiyonlandırılması
Dosyalar
Tarih
2015-02-20
Yazarlar
Atıcı, Lale Nur
Süreli Yayın başlığı
Süreli Yayın ISSN
Cilt Başlığı
Yayınevi
Fen Bilimleri Enstitüsü
Institute of Science and Technology
Institute of Science and Technology
Özet
Bu çalışmada, ilk olarak butiloksanorbornen monomeri Grubbs katalizörü eşliğinde halka açılma metatez polimerizasyonu yöntemi ile polimerleştirildi ve brom ile reaksiyonu gerçekleştirildi. Sonrasında, brom fonksiyonlu PBONB ve akrilat fonksiyonlu TEMPO arasında click reaksiyonu, ilgili aşı polimerini elde etmek amacıyla ATNRC yöntemi ile PMDETA, CuBr ve Cu (0) katalizör sistemi varlığında gerçekleştirildi. PEG-OH ve süksinik anhidritin reaksiyonu ile karboksilik asit fonksiyonlu PEG (PEG-COOH) sentezlendi. Sonrasında, PEG-COOH ve 4-hidroksi-TEMPO arasında, nitroksi radikal fonksiyonlu PEG (TEMPO-PEG) elde etmek amacıyla reaksiyon gerçekleştirildi.Brom fonksiyonlu PBONB ve PEG fonksiyonlu TEMPO arasında click reaksiyonu, ilgili aşı polimeri sentezlemek amacıyla ATNRC yöntemi ile gerçekleştirildi.Epoksi fonksiyonlu PBONB, 4-glycidyl-2,2,6,6-tetramethylpiperidin-1-oxyl ile PBONB-bromide arasında ATNRC reaksiyonu ile sentezlendi. PBONB brom fonksiyonu, ilgili aşı polimerini elde etmek amacıyla ATNRC yöntemi ile PMDETA, CuBr ve Cu (0) katalizör sistemi varlığında epoksi halkasına dönüştürüldü. Son olarak, brom fonksiyonlu PBONB herhangi bir TEMPO grubu kullanılmadan , PMDETA, CuBr ve Cu (0) katalizör sistemi varlığında reaksiyon ortamına konuldu. Orijinal polimerdeki vinilik sinyalin tekrar ortaya çıktığı ve polimerin tamamen orijinal yapısına döndüğü gözlemlendi.
In this thesis, butyloxanorbornene monomer was first polymerized via ring opening metathesis polymerization (ROMP) using the first generation Grubbs’ catalyst in chloroform at room temperature and then, bromine were reacted with PBONB in chloroform at room temperature for 4h . Afterward bromide functionalized PBONB clicked with acrylate functionalized TEMPO via Atom Transfer Nitroxide Radical Coupling (ATNRC) reaction in the presence of PMDETA, CuBr and Cu (0) catalyst system and DMF as solvent , to create corresponding graft polymer, poly(BONBacrylate). Subsequently, thiophenol functionalized polybutyloxanorbornene was successfully prepared by using nucleophilic (Michael) thiol-ene “click” reaction. Next, mono carboxylic acid functional PEG (PEG-COOH) was synthesized with a reaction of PEG-OH in the presence of succinic anhydride. Afterward, PEG-COOH and 4-hydroxy-TEMPO were reacted to obtain nitroxyl radical functionalized PEG (TEMPO-PEG). Then, bromide functionalized PBONB clicked with PEG functionalized TEMPO via ATNRC reaction in the presence of PMDETA, CuBr and Cu (0) catalyst system and DMF as solvent , to create corresponding graft polymer, poly(BONB-PEG). Afterward, epoxy functionalized poly(BONB) was carried out by ATNRC reaction between 4-glycidyl-2,2,6,6-tetramethylpiperidin-1-oxyl and poly(BONB-bromide). The Bromide functionality of PBONB was converted to epoxy in the presence of PMDETA, CuBr and Cu (0) catalyst system and DMF as solvent in order to give poly(BONB-epoxy). Finally, the ATNRC reaction of PBONB-bromide was carried out using without TEMPO groups in the presence of Cu(0), Cu(Br) and PMDETA catalyst system and DMF as solvent at room temperature for 24 h. We observed the original signals belong to PBONB which means in this condition bromine functionalized polymer completely turned into original form.
In this thesis, butyloxanorbornene monomer was first polymerized via ring opening metathesis polymerization (ROMP) using the first generation Grubbs’ catalyst in chloroform at room temperature and then, bromine were reacted with PBONB in chloroform at room temperature for 4h . Afterward bromide functionalized PBONB clicked with acrylate functionalized TEMPO via Atom Transfer Nitroxide Radical Coupling (ATNRC) reaction in the presence of PMDETA, CuBr and Cu (0) catalyst system and DMF as solvent , to create corresponding graft polymer, poly(BONBacrylate). Subsequently, thiophenol functionalized polybutyloxanorbornene was successfully prepared by using nucleophilic (Michael) thiol-ene “click” reaction. Next, mono carboxylic acid functional PEG (PEG-COOH) was synthesized with a reaction of PEG-OH in the presence of succinic anhydride. Afterward, PEG-COOH and 4-hydroxy-TEMPO were reacted to obtain nitroxyl radical functionalized PEG (TEMPO-PEG). Then, bromide functionalized PBONB clicked with PEG functionalized TEMPO via ATNRC reaction in the presence of PMDETA, CuBr and Cu (0) catalyst system and DMF as solvent , to create corresponding graft polymer, poly(BONB-PEG). Afterward, epoxy functionalized poly(BONB) was carried out by ATNRC reaction between 4-glycidyl-2,2,6,6-tetramethylpiperidin-1-oxyl and poly(BONB-bromide). The Bromide functionality of PBONB was converted to epoxy in the presence of PMDETA, CuBr and Cu (0) catalyst system and DMF as solvent in order to give poly(BONB-epoxy). Finally, the ATNRC reaction of PBONB-bromide was carried out using without TEMPO groups in the presence of Cu(0), Cu(Br) and PMDETA catalyst system and DMF as solvent at room temperature for 24 h. We observed the original signals belong to PBONB which means in this condition bromine functionalized polymer completely turned into original form.
Açıklama
Tez (Yüksek Lisans) -- İstanbul Teknik Üniversitesi, Fen Bilimleri Enstitüsü, 2015
Thesis (M.Sc.) -- İstanbul Technical University, Institute of Science and Technology, 2015
Thesis (M.Sc.) -- İstanbul Technical University, Institute of Science and Technology, 2015
Anahtar kelimeler
Atom Transfer Nitroksit Radikal Birleşmesi Reaksiyonu,
Atom Transfer Nitroxide Radical Coupling Reaction