Çeşitli bisfenollerden polisülfon sentezi ve karakterizasyonu
Synthessis of polysulphone from di̇fferent type bisphenols
- Tez No: 356096
- Danışmanlar: PROF. NİLGÜN KIZILCAN
- Tez Türü: Yüksek Lisans
- Konular: Kimya, Chemistry
- Anahtar Kelimeler: Belirtilmemiş.
- Yıl: 2014
- Dil: Türkçe
- Üniversite: İstanbul Teknik Üniversitesi
- Enstitü: Fen Bilimleri Enstitüsü
- Ana Bilim Dalı: Kimya Ana Bilim Dalı
- Bilim Dalı: Belirtilmemiş.
- Sayfa Sayısı: 81
Özet
İki fenolün çekirdeklerinin hidrokarbon köprüsüyle birbirine bağlandığı bileşikler olarak tanımlanan bisfenoller 1930'lu yılların sonunda birçok alanda kullanılmaya başlanmıştır. Bisfenoller termal dayanımı yüksek polimerlerin elde edilmesinde, epoksi reçinelerin üretiminde, boya ve cilaların hazırlanmasında önemli bir yere sahiptir. Polisülfonlar; yüksek sıcaklıklara dayanıklılık, sertlik, iyi mekanik özellikler gibi kayda değer ölçüde yararlı özelliklere sahip yüksek yapılı polimerlerdir. Yüksek sıcaklıklarda asitlere, bazlara ve hidrolize karşı direnç gösterirler. Polisülfonlar bu özelliklerinden dolayı biyokimya, gıda endüstrisi, medikal endüstri, otomobil endüstrisi gibi birçok alanda kullanılırlar. Uygulama yapılan alana göre polisülfonlara kimyasal ve fiziksel özellikler eklenmek istediğinde bu iki yolla modifikasyonları gerçekleştirilir. Polisülfonların modifikasyonunda; 1) Monomerlerin fonksiyonlandırılması ve daha sonra polimer elde edilmesi 2) Polisülfon polimerinin fonksiyonlandırılıp, daha sonra başka polimerler ile birleştirilmesi yöntemleri kullanılır. Günümüzde polisülfonların film olabilme özelliklerinden yararlanılmaktadır. Polisülfonların gözenek kontrolü kolaydır ve tekrar üretilebilirler. Bu özelliklerinden dolayı membran olarak da kullanılmaktadırlar. Bu çalışmada; bisfenol A, bisfenol AP ve bisfenol CD monomerleri sentezlenerek, bu monomerlerden ayrı ayrı polisülfon elde edilmiştir. Monomerler, Fourier transform infrared (FTIR), nükleer manyetik rezonans (NMR) spektrometrisi, gaz kromatografisi ve kütle spektrometrisi (GC - MS) yöntemleri ile karakterize edilmiştir. Differansiyel taramalı kalorimetre (DSC) ile monomerlerin erime noktaları tayini yapılmıştır. Sentezlediğimiz üç farklı bisfenolün, ayrı ayrı bis (p-klorofenil) sülfon ile azot atmosferinde 150ºC de 4 saat süren reaksiyonu sonucunda polisülfon sentezlenmiştir. Polisülfon sentezinde iki farklı monomer oranı kullanarak altı farklı polisülfon elde edilmiştir. Polisülfon sentezinde bisfenol A en çok kullanılan monomerdir. Bizim çalışmamızda ise bisfenol CD, bisfenol AP polisülfon sentezinde ilk kez kullanılmıştır. Elde edilen polimerlerin monomerlerinin farklı olmasından dolayı özellikleri karşılaştırılmıştır. Polisülfonlar da benzer şekilde, Fourier transform infrared (FTIR), nükleer manyetik rezonans (NMR) spektrometresi, diferansiyel taramalı kalorimetre (DSC) ve jel geçirgenlik kromatografisi (GPC) yöntemleri ile karakterize edilmiştir. Polimerlerin; camsı geçiş sıcaklığı, DSC ile belirlenmiştir. DSC sonuçları değerlendirildiğinde bisfenol CD polisülfona bağlanan alifatik grubun esneklik getirerek camsı geçiş sıcaklığını azalttığı, bisfenol AP'de ise eklenen grubun polisülfon yapısındaki sertliği arttırarak camsı geçiş sıcaklığını arttırdığı gözlenmiştir.
Özet (Çeviri)
Bisphenol are defined as a compound containing of two phenols nuclei linked by a hydrocarbon bridge. The importance of bisphenols has increased continually with the growth of the plastic from about the end of the 1930 s. Bisphenol have been synthesized by condensation with cyclic ketones, aliphatic ketones, aldehyde and acetophenon in the presence of various catalysts. Although these methos are suitable for but many of these methods are associated with one more disadvantages such as, prologed reaction time, harsh reaction conditions and unsatisfactory yields, use of halogenated hydrocarbons solvent, excess use of phenols tedious work up, charcoalization, and generation large quantitiy of hazardous phenolic residue, multistep purifications and heavy pollution of chlorinated solvents. Bisphenols are useful for the preparation of thermally stable polymer, epoxy resin, paint and varnishes. The condensation products of phenols with cyclic hydroaromatic ketones are known as cardo (a loop) monomer. The monomer containing cardo group are very useful in synthesizing polymer with very specific properties such as enhanced backbone structure. Bisphenols are useful for the preparation of polycarbonates that are useful as binders for charge transport molecules, and photogenerating pigments incorporated, for example in to layered photoconductive imaging member. Polysulfone (PSU) is a high performance thermoplastic with significant properties such as, thermally and oxidatively stable at higher temperatures, good mechanical properties, high glass transition temperatures, high strength and stiffness at high temperatures, continuously use, perfect resistance to acids and bases. PSU offers good film forming properties as well. Recently researchers are benefitted from the film forming properties of polysulfones. Due to ease of manufacturing of reproducible membranes having controlled pore sizes PSU polymers finds places in membrane technology such as hemodialysis, water purification, gas separation and fuel cells. Also PSU polymers have been used in preparation of block copolymers after postmodification of their side chains or terminal groups with functional groups that may be used in polymerization of monomers or in chemical bonding with other polymers. End functionalized PSU polymers or oligomers are also used in combination with thermosets based on epoxy resins for dissolving the problem related to brittleness. Due to these superior features, PSU have been applied in many different applications, such as automotive parts, food processing systems, medical equipments, feeding technology and electronic industry. Depends upon the area of application , materials with additional physical and chemical properties can be obtained by the modification of polysulfone polymers. Functionalization of polysulfone polymers may be achieved two general ways; i) Firstly monomers are fuctionalized and then copolymerized, ii) Postpolymerization technique in which PSU polymer is modified with other functional group or polymers are obtained. However, they have several disadvantages such as higher solvent sensivities, creeping under load at high temperatures above their Tg's susceptible to stress cracking with certain solvents, the non-resistance to ultra violet (UV) radiations, poor tracking resistance and poor weathering properties, which may limit their uses suchs as in blood filtration its hydrophobicity causes fouling of the proteins. Without losing the polymer properties, chemical modifications of the end groups or polymer backbone of polysulfones gave good results as compared to the blended systems, in which two or more different polymers combine to get new polymeric systems for specific purposes. After chemical modifications these polymers can be used many different industrial areas such as automobiles, electronics, aerospace, membrane etc. First part of this study, bisphenol A, bisphenol AP and bisphenol CD are synthesized. After the monomer synthesized, they are characterized by Fourier transform infrared (FTIR), nuclear magnetic resonance (NMR), gas chromatography- mass spectroscopy (GC-MS) and differential scanning calorimetry (DSC). The result of these analysis are compared to each other. Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) showed that we could synthesize bisphenols. We had two kind of nuclear magnetic resonance analysis for these bisphenols such 1H NMR and 13C NMR. We could confirm the structures are obtained with three of these analysis methods. Gas chromatography- mass spectroscopy showed that synthesized monomers are pure and their molecule weight as same as literature. Three of these monomers melting point (Tm) are determined by differantial scanning calorimetry (DSC). And we compared how that melting point effects polysulfone features. Second part of this study; different kind of polysulfones are synthesized by using different bisphenol such as, bisphenol A, bisphenol AP and bisphenol CD. Bisphenol A is a well known polymer material and it is synthesized commercially. Bisphenol AP polysulfone and bisphenol CD polysulfone are synthesized first time in that study. We compared how their features change when we modify with another monomer them. The synthesis of these polysulfones was under reflux system at 150 ºC for 4 hours with water removal. DMAC and toluene were used as solvent and also K2CO3 added in the reaction. Thirth part of this study; rate of monomer are changed and determined polysulfones which have different molecule weight. 2:1 rate bisphenol : bis (p-chlorophenylsulfone). And totally six type polysulfone were synthesized. All polysulfones which are synthesized are characterized by Fourier transform infrared (FTIR), nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC) and gel permeation chromatography (GPC). Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) showed that we could synthesize bisphenols succesfully. We had two kind of NMR analysis for these polysulfones as 1H NMR and 13C NMR to characterize polysulfone backbone. Polysulfones glass transition (Tg) are determined by differantial scanning calorimetry (DSC). We compared how glass transition will change when we use different kind of bisphenol as monomer. Polysulfone molecule weight are determined by gel permeation chromatography (GPC). We were compared how features such as glass transition could effect on molecule weight. Results of gel permeation chromatography (GPC) showed that the molecule weights are less than expect to be sytnthesized. As it is a condensation reaction, if reaction occurs longer time than six hours, polymers which have high molecule weight can be obtained. On the other hand, dispersity of the polymer that are synthesized, are close to 1. 1 is ideal rate for being homogeneous. It can be said that polymers are synthesized in that study close to be homogeneous.
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