Please use this identifier to cite or link to this item: http://hdl.handle.net/11527/12933
Title: Poli(bütil Akrilat-metil Metakrilat) Nanokompozitlerin Film Özelliklerinin İncelenmesi Ve Boya Bağlayıcısı Olarak Kullanımı
Other Titles: Investigation Of Poly(butyl Acrylate-co-methyl Methacrylate) Nanocomposite Film Properties And Its Uses As Paint Binder
Authors: Sirkecioğlu, Ahmet
Vatansever, Alican
10079793
Kimya Mühendisliği
Chemical Engineering
Keywords: poli(bütil akrilat-ko-metil metakrilat)
nanokompozit
montmorillonit
nanokristalin selüloz
yol çizgi boyası
poly(butyl acrylate-co-methyl methacrylate)
nanocomposite
montmorillonite
nancrystalline cellulose
road marking paint
Issue Date: 15-Jul-2015
Publisher: Fen Bilimleri Enstitüsü
Institute of Science And Technology
Abstract: Poli(bütil akrilat-ko-metil metakrilat)(poli(BA-ko-MMA) iyi film oluşturabilme özelliği sayesinde kaplama malzemelerinde, verniklerde, yapıştırıcı ve benzeri malzemelerde bağlayıcı olarak kullanılan bir kopolimerdir. Genel olarak polimer filmlerin özelliklerini geliştirmek için nano boyutta katkılar ile gerçekleştirilen nanokompozit sentezi son 20 yılın en önemli çalışma alanlarından biri olmuştur. Bu çalışmanın ilk aşamasında su bazlı yol çizgi boyalarında bağlayıcı olarak kullanılabilecek poli(BA-ko-MMA) sentezi gerçekleştirilmiştir. Kopolimerin sentezi yarı kesikli emülsiyon polimerizasyonu ile gerçekleştirilmiştir. İstenilen camsı geçiş sıcaklığı ve molekül ağırlıklarında kopolimer sentezlenebilmesi için gerekli koşullar belirlenmiştir. Çalışmanın daha sonraki aşamalarında sentezlenen su bazlı bağlayıcıya çeşitli nano katkılar ilave edilmiştir. • Reşadiye bölgesinden temin edilen sodyum bentonitin saflaştırılması ile Na-montmorillonit (Na-Mt) elde edilmiş olup % 1-3 arasında değişen oranlarda Na-Mt katkısı ile poli(BA-ko-MMA) nanokompozit sentezi gerçekleştirilmiştir. Yarı kesikli yerinde emülsiyon polimerizasyonu yöntemi ile % 47 katı madde içeriğine sahip nanokompozitler elde edilmiştir. Karşılaştırma amaçlı % 35 katı madde içerikli nanokompozit ile poli(BA-ko-MMA) kopolimerinin Na-Mt süspansiyonu ile doğrudan karıştırıldığı (harmanlama yöntemi) nanokompozitler de hazırlanmıştır. • Farklı yapılardaki 5 kuaterner amonyum tuzu kullanılarak Na-Mt’nin modifikasyonu sonucu Organo-montmorillonit (O-Mt) üretimi gerçekleştirilmiştir. Bu O-Mt’ler kullanılarak yarı kesikli yerinde emülsiyon polimerizasyonu ile poli(BA-ko-MMA) nanokompozitleri sentezlenmiştir. Diğer çalışmalardan farklı olarak bu çalışmada O-Mt’ler, Na-Mt’nin modifikasyonundan hemen sonra süspansiyon halinde nanokompozit sentezinde kullanılmıştır. Bu sayede emülsiyon polimerizasyonu ile O-Mt temelli su bazlı nanokompozit sentezinin yanısıra % 47 gibi yüksek katı madde oranı da elde edilmiştir. O-Mt nanokompozit çalışmalarında da karşılaştırma amaçlı % 35 katı madde içerikli nanokompozitler ve harmanlanmış nanokompozitler hazırlanmıştır. • Mikrokristalin selülozun (MKK) asit hidrolizi sonucu elde edilen nanokristalin selüloz da poli(BA-ko-MMA) kopolimerinde katkı olarak kullanılmıştır. Harmanlama yöntemi ile hazırlanan NKS temelli poli(BA-ko-MMA) nanokompozitlerin NKS içerikleri % 1-3 arasında değişip katı madde oranı % 35’tir. Na-Mt, O-Mt ve NKS katkılı poli(BA-ko-MMA) kopolimerlerin tane boyut dağılımları, molekül ağırlıkları, camsı geçiş sıcaklıkları belirlenmiş, X-ışınları difraktometrisi (XRD), taramalı elektron mikroskobu (SEM), geçirimli elektron mikroskobu (TEM), infrared spektrofotometresi (FT-IR), Termogravimetrik analizi (TGA) ile karakterizasyon testleri yapılmış ve mekanik testler ile mukavemetleri ölçülmüştür. Gerçekleştirilen karakterizasyon ve testler sonucunda montmorillonit katkılarının polimer performansını olumlu yönde etkilediği belirlenmiştir. Ancak O-Mt’lerin poli(BA-ko-MMA) daha iyi uyum sağladığı anlaşılmıştır. NKS esaslı poli(BA-ko-MMA) nanokompozitlerin mekanik mukavemeti daha yüksek bulunmuştur. Montmorillonit katkıları kopolimerin çekme gerilimini % 187,5 arttırırken NKS % 262,5 arttırmıştır. Daha sonra optimum özelliklerde nanokompozit elde etmek için % 1,5 NKS ve % 1,5 Na-Mt katkılı kopolimer de sentezlenmiştir. Çalışmanın son aşamasında katkısız ve montmorillonit katkılı poli(BA-ko-MMA) kopolimerin bağlayıcı olarak kullanıldığı su bazlı yol çizgi boyaları hazırlanmıştır. Üretilen yol çizgi boyalarının Karayolları Genel Müdürlüğü’nün istediği standartlarda olduğu örtme, yüzey kuruma, dip kuruma, aşınma direnci ve kromatiklik koordinatları gibi boya testleri ile belirlenmiştir. Montmorillonit, kopolimerin film özelliklerini geliştirmiştir. Ancak katkısız kopolimerli bağlayıcı ile montmorillonit bazlı nanokompozit bağlayıcının kullanıldığı boyaların özellikleri arasında önemli bir fark görülmemiştir.
Poly(butyl acrylate-co-methyl methacrylate) (poly(BA-co-MMA) is a copolymer used as a binder in coating materials, lacquers and glue-like materials by means of to its good film forming properties. Generally, for two decades, many studies have been devoted to nano-reinforcement addition into polymers for improving features of polymer films. In this study first of all poly(BA-co-MMA) was synthesized in order to be used as binder in water based road marking paint. The synthesis of the copolyme rwas conducted by semi batch emulsion polymerization. Necessary conditions were determined in order to synthesize copolymer with intented glass tarnsition temperature and molecular weight. In the later stage of the study, different nano additives were added to the water based binder. Natural sodium montmorillonite, Na-Mt, is the most used smectite clay for polymer-clay nanocomposite (PCN) synthesis. The thickness and width of Na-Mt crystals are 1 nm and 200-600 nm, respectively. A PCN can be obtained by dispersing Na-Mt in a polymer matrix. PCNs are mainly synthesized by four processes; exfoliation-adsorption,template synthesis, melt intercalation and in situ intercalative polymerization.In order to synthesize waterborne PCNs, in situ intercalative polymerization is considered to be most suitable method. For a waterborne PCN with improved properties, Na-Mt should sufficiently disperse in the polymer matrix. Na-Mt is fully hydrated in water. Therefore, in-situ emulsion polymerization is commonly preferred for waterborne PCN synthesis. Since most of the monomers/polymers are hydrophobic, hydrophilic feature of Na-Mt can be altered to form organo modified montmorillonite (O-Mt) by exchange of Na+ with organic cations as quaternary ammonium cations. Those exchanged organic cations can increase interlayer spacing of Na-Mt, leading to enhance polymer intercalation or even form highly exfoliated nanocomposites. • In this study, Na-Montmorillonite (Na-Mt) was obtained by purificaion of sodium bentonite available from Resadiye. Poly(BA-co-MMA) nanocomposite synthesis was achieved with Na-M contents ranging between 1-3 %. Nanocomposites having 47 % solids content were obtained via semi batch in-situ emulsion polymerization. For comparison, nanocomposite having 35 % solids content and nanocomposite, which was prepared by direct blending of Poly(BA-co-MMA) and Na-Mt, were synthesized (blend process). • Na-Mt was modified with five different quaternary ammonium salts and organo-montmorillonites (O-Mt) were formed. By using these O-Mts poly(BA-co-MMA) nanocomposite was synthesized via semi batch in-situ emulsion polymerization. Differing from other studies, in this thesis O-Mt was used in suspension form for nanocomposite synthesis directly after the modification of Na-Mt. By this way, water based O-Mt nanocomposites with 47 % solids contents were obtained via emulsion polymerization. Like Na-Mt nanocomposites, also an O-Mt nanocomposite having 35 % solids content was synthesized and an O-Mt nanocomposite was prepared by blend process for comparison. • In the last years, the production of nano cellulose fibers and their applications in the polymers have gained increasing attention. Instead of card structure of clay, CNCs are long crystalline needles (tens to hundreds of nanometers) ranging in size from 1 to 20 nm in width. Nanocrystalline cellulose (NCC), which was obtained by acid hydrolysis of microcrystalline cellulose (MCC), was used as an additive in poly(BA-co-MMA). NCC based nanocomposites were prepared by blend process. NCC ratio varied between 1-3 % and solids content of the nanocomposite was 35 %. Size distributions, molecular weights, glass transition temperatures of Na-Mt, O-Mt and NCC based nanocomposites were determined, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), infrared spectroscopy (FTIR), thermal gravimetric analyses were performed mechanical properties were investigated by mechanical tests. Average particle sizes of Na-Mt nanocomposites were measured as 110-150 nm while O-Mt nanocomposites were measured as 200-350 nm. According to the characterization and tests, it was found out that montmorillonite additives improved copolymer properties. Stable nanocomposites with 35 wt. % solids content and 3 wt. % Na-Mt or O-Mt content were obtained without any coagulum. The synthesis of nanocomposite containing 47 wt. % solids was also achieved, but slight coagulum (1-4 %) formed at high Mt contents. As a result, the poly(BA-co-MMA)-Mt nanocomposite containing the highest solid and Mt content in the literature was synthesized. Furthermore, waterborne nanocomposites were prepared by blending pure copolymer latex with Na-Mt or O-Mt. However, O-Mt blend showed weak properties relative to Na-Mt blend and the other O-Mt based nanocomposites. DSC results revealed that the addition of Mt particles increased glass transition temperature of the copolymer slightly. The decomposition temperatures of the nanocomposites clearly increased with the addition of Mt particle according to TGA results. In the mechanical testing studies, tensile strength and storage modulus of all nanocomposites were higher than the pure copolymer while elongation at break decreased slightly for the films containing Na-Mt. Mechanical tests showed that exfoliated morphologies enhanced mechanical properties exceptionally relative to the intercalated/aggregated morphologies. All of the nanocomposites exhibited improved barrier properties in terms of WVTR. Oxygen permeability test also revealed that Na-Mt and O-Mt additive decreased oxygen permeability. The gloss values of O-Mt nanocomposites were found to be higher than that of the pristine copolymer, whereas Na-Mt nanocomposites exhibited less brightness. Consequently, elongation at break, barrier and gloss results exhibited that compatibility between O-MMT and copolymer was higher when compared to Na-MMT. As a result, it was realized that O-Mts showed higher affinity towards poly(BA-co-MMA) than Na-Mt. NCC improved tensile strength much higher and reached a maximum at the highest content. Tensile strength of montmorillonite based nanocomposite increased 187.5 % while tensile strength of NCC nanocomposite increased 262.5 %. With the idea of obtaining optimum values, 1.5 % NCC and 1.5 % Na-Mt were also added to poly(BA-co-MMA). Finally, water based road marking paints were prepared in which pristine copolymer and montmorillonite reinforced copolymers were used as binders. These road marking paints were in the limits of the General Directorate of Highways standards according to the dye tests of hiding power solid dry time, no pick up time, abrasion resistance and chromaticity coordinates. Although montmorillonite enhanced latex film properties, no effect was observed in the properties of paint which had been produced by using montmorillonite based nanocomposite as binder.
Description: Tez (Doktora) -- İstanbul Teknik Üniversitesi, Fen Bilimleri Enstitüsü, 2015
Thesis (PhD) -- İstanbul Technical University, Institute of Science and Technology, 2015
URI: http://hdl.handle.net/11527/12933
Appears in Collections:Kimya Mühendisliği Lisansüstü Programı - Doktora

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