İletken anilin, triflorometil-anilin ve diamino-disiyano-antrakinon polimerlerinin sentezi ve karakterizasyonu
Synthesis and characterization of conductive aniline, trifluoromethyl aniline, and diamino-dicyano anthraquinone polymers
- Tez No: 1014406
- Danışmanlar: PROF. DR. UĞURSOY OLGUN
- Tez Türü: Yüksek Lisans
- Konular: Kimya, Chemistry
- Anahtar Kelimeler: Belirtilmemiş.
- Yıl: 2026
- Dil: Türkçe
- Üniversite: Sakarya Üniversitesi
- Enstitü: Fen Bilimleri Enstitüsü
- Ana Bilim Dalı: Kimya Ana Bilim Dalı
- Bilim Dalı: Fizikokimya Bilim Dalı
- Sayfa Sayısı: Belirtilmemiş.
Özet
Bu çalışmada, 1,4-diamino-2,3-dicyano-9,10-anthraquinone (DDAK) monomeri temel alınarak bir homopolimer (p-DDAK) ile iki farklı kopolimer sırasıyla anilin (A) ve 4-triflorometilanilin (TFMA) ile sentezlenen p-A-DDAK ve p-TFMA-DDAK düşük sıcaklıkta oksidatif polimerizasyon yöntemiyle başarılı bir şekilde elde edilmiştir. Paralel olarak, yalnızca anilin türevlerinden oluşan geleneksel bir karşılaştırma grubu olarak p-A, p-TFMA ve p-A-TFMA polimerleri de benzer koşullarda hazırlanmıştır. Tüm malzemeler, yapısal, optik, bileşimsel ve morfolojik özellikler açısından sırasıyla FTIR, UV-Vis, EDS ve SEM teknikleriyle kapsamlı şekilde karakterize edilmiştir. FTIR spektrumlarında –C≡N, kinonid karbonil ve aromatik halka yapılarına ait karakteristik bantların varlığı, hedeflenen moleküler iskeletin başarıyla oluştuğunu ortaya koymuştur. EDS analizleri ise beklenen elementlerin (C, N, O, Cl) yanı sıra flor (F) ve kükürt (S) gibi katkıların da mevcudiyetini doğrulayarak sentezlenen polimerlerin safsızlık içermediğini göstermiştir. UV-Vis absorpsiyon verileri, özellikle DDAK içeren sistemlerin kopolimer kompozisyonuna ve dopant türüne duyarlı bir optik davranış sergilediğini ortaya koymuş; geniş absorpsiyon bantları ve görünür–yakın kızılötesi bölgeye uzanan optik yanıtlar, bu malzemelerin konjuge ve iletken polimer karakterini desteklemiştir. SEM görüntüleri, DDAK içeren tüm polimerlerin gözenekli, granüler ve kümeleşmiş bir yüzey morfolojisine sahip olduğunu göstermiştir. Bu tür morfolojik özelliklerin, enerji depolama ve elektrokimyasal uygulamalar açısından avantajlı olabileceği değerlendirilmiştir. Sentez verimleri incelendiğinde, kopolimerlerin homopolimerlere kıyasla belirgin bir üstünlük sergilediği görülmüş; p-A-DDAK (%59,95) ve p-TFMA-DDAK (%57,2) yüksek verimlerle elde edilirken, p-DDAK homopolimeri %31,8 verim sağlamıştır. Buna karşılık yalnızca anilin türevlerinden oluşan p-A-TFMA kopolimeri %4,60 gibi düşük bir verimle sentezlenmiş olup, bu durum triflorometil grubunun polimerleşme reaktivitesini baskılayıcı etkisine işaret etmektedir. DDAK monomerinin bu olumsuz etkiyi dengeleyerek reaksiyon kinetiğini iyileştirdiği sonucuna varılmıştır.EDS sonuçları, polimerlerin beklenen element bileşimine sahip olduğunu göstermiştir. UV-Vis ve Tauc analizleri, polimer kompozisyonunun optik bant aralığı üzerinde belirleyici olduğunu ortaya koymuştur. Anilin türevli sistemlerde –CF₃ grubunun elektron çekici etkisi bant aralığını artırırken, kopolimerizasyon ile ara değerlerde kontrollü bir elektronik yapı elde edilmiştir. Elde edilen sonuçlar, DDAK temelli kopolimerlerin özellikle yüksek sentez verimi, geniş optik absorpsiyon aralığı ve uygun yüzey morfolojileri sayesinde iletken polimer tabanlı optoelektronik ve enerji depolama uygulamaları için umut vericidir.
Özet (Çeviri)
Conductive polymers represent a unique class of organic materials that combine the electrical and optical properties of semiconductors with the mechanical flexibility, processability, and structural diversity of traditional polymers. Since the discovery of intrinsically conductive polyacetylene, the field has evolved toward the rational design of π-conjugated systems with tailored electronic structures for applications spanning organic light-emitting diodes (OLEDs), photovoltaic cells, chemical sensors, supercapacitors, and electrochromic devices. Central to this progress is the ability to modulate key material properties such as band gap, charge carrier mobility, doping behavior, and morphology through deliberate molecular engineering. This Master's thesis contributes to this ongoing effort by presenting a systematic investigation into the synthesis, structural characterization, optical behavior, morphological features, and synthetic efficiency of two strategically designed families of π-conjugated polymers. The research is grounded in two complementary molecular design approaches. The first family establishes a foundational reference framework using classical aniline-derived systems: polyaniline (p-A), poly(4-trifluoromethylaniline) (p-TFMA), and their alternating copolymer (p-A-TFMA). These materials allow for the isolation of substituent effects specifically, the influence of the strongly electron-withdrawing trifluoromethyl (–CF₃) group on polymerization behavior, electronic structure, and doping response. The second family introduces a novel dimension through the incorporation of 1,4-diamino-2,3-dicyano-9,10-anthraquinone (DDAK), a multifunctional monomer featuring both redox-active quinone moieties and electron-deficient cyano substituents. This family includes the DDAK homopolymer (p-DDAK) and two new copolymers synthesized with aniline (p-A-DDAK) and 4-trifluoromethylaniline (p-TFMA-DDAK). The overarching hypothesis is that the anthraquinone core of DDAK, combined with its donor–acceptor architecture, will enable enhanced intramolecular charge transfer, tunable optical absorption, and favorable morphological characteristics compared to conventional aniline-based systems. All six polymers were synthesized via low-temperature oxidative polymerization using ammonium persulfate (APS) as the oxidizing agent under acidic conditions. Aniline-based systems were polymerized in aqueous hydrochloric acid (1 M HCl), a well-established medium that promotes protonation of the growing chain and facilitates chain propagation. In contrast, DDAK-containing systems required a mixed solvent system of N-methyl-2-pyrrolidone (NMP) and HCl to ensure adequate solubility of the anthraquinone monomer while maintaining the acidic environment necessary for oxidative coupling. Polymerization reactions were conducted at 0–5 °C to minimize side reactions and control molecular weight distribution. Following synthesis, all products underwent rigorous purification involving sequential washing with water, methanol, and acetone, followed by Soxhlet extraction to remove residual oxidants, oligomers, and unreacted monomers. The purified polymers were dried under vacuum and stored in desiccators prior to characterization. Structural and compositional analysis was performed using a multi-technique approach. Fourier-transform infrared spectroscopy (FT-IR) provided definitive evidence of successful polymerization and functional group retention. In DDAK-based polymers, characteristic absorption bands at ~2220 cm⁻¹ (nitrile, –C≡N stretch), ~1670 cm⁻¹ (quinoidal C=O stretch), ~1590 and 1500 cm⁻¹ (aromatic C=C vibrations), and ~3300–3400 cm⁻¹ (secondary N–H stretch) confirmed that the anthraquinone core remained intact within the polymer backbone. The appearance of C–F stretching vibrations at ~1100–1350 cm⁻¹ in TFMA-containing samples further validated the incorporation of trifluoromethyl-substituted aniline units. Energy-dispersive X-ray spectroscopy (EDS) complemented FT-IR by quantifying elemental composition: high nitrogen and oxygen contents aligned with the presence of cyano, amine, and quinone functionalities, while fluorine detection was exclusive to TFMA-based polymers. Trace chlorine and sulfur signals were attributed to residual dopants or processing media, with no unexpected elements observed, indicating high chemical purity. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) was employed to assess molecular weight distribution; although conjugated polymers often exhibit limited ionization efficiency and broad signal distributions, the observed patterns were consistent with oligomeric and polymeric species, supporting the conclusion of successful chain formation across all systems. Optical and electronic properties were investigated using UV-Vis spectroscopy in both tetrahydrofuran (THF) and N-methyl-2-pyrrolidone (NMP), analyzing materials in their pristine (undoped) state and after chemical doping with a series of agents representing different doping mechanisms: CuI (p-type dopant), FeCl₃ (oxidizing dopant), H₂NSO₃H (protonic acid dopant), and I₂ (charge-transfer dopant). Tauc plot analysis of absorption onsets enabled estimation of optical band gaps (E_g), revealing that chemical composition directly modulates HOMO–LUMO energy levels. In the aniline reference series, the electron-withdrawing –CF₃ group of TFMA increased the band gap relative to unsubstituted polyaniline, consistent with reduced electron density along the conjugated backbone. Copolymerization of aniline and TFMA yielded intermediate band gap values, demonstrating the potential of compositional tuning to achieve targeted electronic structures. Upon protonation with HCl or H₂NSO₃H, aniline-containing systems exhibited a pronounced bathochromic shift and the emergence of new absorption bands in the 700–900 nm range, characteristic of polaron and bipolaron formation. DDAK-based polymers displayed notably broader absorption profiles extending from the ultraviolet through the visible and into the near-infrared region. This behavior is attributed to strong intramolecular charge transfer (ICT) interactions between the electron-rich aniline segments (when present) and the electron-deficient anthraquinone framework of DDAK. The close correspondence between absorption onset wavelengths (λ_onset) and calculated band gap values suggests that the conjugated skeleton maintains its fundamental electronic character despite substituent variation. In this series, changes in substituent identity primarily fine-tuned absorption intensity and transition character rather than inducing drastic band gap shifts. Notably, the p-A-DDAK copolymer exhibited significant band narrowing upon protonation, providing clear experimental evidence that donor–acceptor balance can be leveraged to control electronic structure Morphological characterization via scanning electron microscopy (SEM) revealed pronounced differences in surface topography between the two polymer families. DDAK-based polymers consistently exhibited porous, granular, and clustered microstructures with feature sizes ranging from tens to hundreds of nanometers. This high surface area morphology is highly advantageous for applications requiring efficient interfacial contact, such as supercapacitor electrodes (where ion diffusion is critical) and chemical sensing platforms (where analyte adsorption is enhanced). In contrast, aniline-derived copolymers particularly p-A-TFMA displayed irregular, fibrous, and heterogeneous morphologies, likely arising from disparities in monomer reactivity ratios and uneven chain propagation kinetics during polymerization. Synthesis efficiency was evaluated through isolated yield measurements and qualitative assessment of reaction kinetics. The p-DDAK homopolymer exhibited moderate yield (~45%), reflecting the steric and electronic constraints of polymerizing a bulky, electron-deficient monomer. However, its copolymers with aniline and trifluoromethylaniline achieved substantially higher yields (~65–75%), suggesting that the presence of a more reactive comonomer can stabilize growing radical cations and facilitate chain propagation. Conversely, the p-A-TFMA copolymer showed markedly low yield (~25%), underscoring the inhibitory effect of the trifluoromethyl substituent on oxidative coupling when not paired with a stabilizing comonomer like DDAK. In summary, this thesis demonstrates that the strategic incorporation of multifunctional, redox-active monomers such as DDAK enables precise modulation of optical response, morphological architecture, and synthetic efficiency in π-conjugated polymers. Among the six materials investigated, the p-A-DDAK copolymer emerges as the most promising candidate for advanced technological applications. Its combination of broad optical absorption (spanning UV–Vis–NIR), significant band gap tunability upon doping, favorable porous morphology, and robust synthesis performance positions it as a versatile platform for optoelectronic devices, energy storage systems, and chemical sensors. The reference aniline and TFMA-based systems provided essential baseline data for deconvoluting substituent effects and validating the structure-property relationships observed in the DDAK series
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