Türkiye kökenli tall-yağı ile inden-kumaron`un özel bir değerlendirilme teknolojisi üzerinde

Abstract

ÖZET Bu çalışmada, yurdumuzun Selüloz ve Kağıt Fabri kaları ile Demir-Çelik İşletmelerinin Kok Fabrikaları gibi İki büyük, sanayi branşının yan ürünlerini değerlendirmek amacı güdülmüştür. Bu amaçla, SEKA Dalaman ve Çaycuma Selüloz ve Ka ğıt Fabrikaları yan ürünü olan Tall-Yağı ile Karabük ve Ereğli Demir-Çelik İşletmeleri Kok Fabrikaları yan ürünü Karbol Yağı nın bir fraksiyonu olan İnden-Kumaron'un reaksiyonundan oluşan ve organik yüzey kaplayicı alanında kullanılabilecek yeni bir ürün elde edilmiştir ve teknolojik özellikleri incelenmiştir. îlk önce, kağıt fabrikalarımızdan Çaycuma îşletme- sinden ham tali yağı ve Dalaman işletmesinden ise sülfat sabunu halinde temin edilmiş olan bu ilkel maddelerin komple analizi, gaz kroma t o gr af i si vasıtasıyla yağ ve reçine asitleri içerikle rinin bileşimleri tespit edilmiştir. Daha sonra, bu ilkel mad delerin rafinasyonu ile Dalaman ve Çaycuma rafine tali yağları ayrı ayrı preparatif olarak elde edilmiştir. Yine, Karabük Demir-Çelik İşletmeleri Kok Fabrika ları Katran Tesislerinden getirtilmiş olan karbol yağı fraksi yonundan önce naftalin, fenoller ve piridin bazlarının gideril mesi yapılarak elde edilen nötr yağ fraksiyonundan, en yüksekVI teknik saflıktaki inden-kumaronu çekmek için bir seri distilas- yon deneyleri yürütülmüştür. Sonuç olarak, nötr yağın 15 mm Hg basıncında 37-79 °C 1ar arası kaynayan kısmı çekilmiştir ve yaklaşık %80'i polimerleşebilen madde olan bu fraksiyon bu ça lışmada teknik inden-kumaron olarak kullanılmıştır. Daha sonra,. Dalaman ve Çaycuma tali yağı örnekleri ile inden-kumaron arasındaki kopolimerizasyon reaksiyonuna tem-, peratür ve ısıtma suresi etkisinin incelendiği deney serilerine ait neticelerin topluca değerlendirilmesiyle, optimum reaksiyon temperatürü ve süresi için sırası ile 240 °C ve 16 saat değerle rinin en uygun olacağı tespit edilmiştir. Böylece Dalaman ve Çaycuma tali yağları ile inden-kumar ondan, sırası ile 73:27 ve 74:26 reaktan oranlarında ve belirlenen optimum koşullarda üre tilen kopolimerizatlarm etilenglikol, gliserol ve pentaeritri tol esterleri ile pentaeritritol esterlerinin izosiyanatları laboratuar ölçüsünde hazırlanmıştır. Hazırlanan bu yeni ürünlerin organik yüzey kapla- yıcısı olarak film özelliklerini karşılaştırmak amacıyla, piş miş keten yağı, pişmiş keten yağıîçin odun yağı (.90;. 10) karı şımı, keten yağı ile modifiye uzun yağlı alki.d reçinesi, keten ve ayçiçeği yağlarının inden-kumaron kopolimerizatları, Dalaman ye Çaycuma rafine tali yağlarının pentaeritritol esterleri ile pentaeritritol esterlerinin izosiyanatları da hazırlanmıştır. Çalışmanın en sonunda ise, elde edilen tüm yeni ürünler ile yukarda açıklanan mukayese ürünlerinin başlıcaVII film özellikleri tespit edilerek birbirleri ile karşılaştı- rılmıştır. Dalaman ve Çaycuma tali yağları inden-kumaron kopolimer i zatlarından elde edilen ürünlerin film özellikleri, bu yeni ürünlerin organik yüzey kaplayıcısı olarak kullanıla bileceğini göstermiştir. Tali yağı ile inden-kumaronun milli sanayimizin birer yan ürünü olduğu düşünülürse, bu çalışma ile, sözü edi len ilkel madde kaynaklarına yeni bir kullanım alanı ortaya konmuştur.

VIII SUMMARY The aim of this study is to find out a more efficient field of utilization concerning the two by-products from two potential Turkish industry branches such as pulp and paper-, and by-product coal cooking plants. For this purpose, the tall oil samples from SEKA Dalaman and Çaycuma Pulp and Paper Mills and indene-coumarone from Karabük Iron-Steel and Coal Coking Plants were obtained and new products were deve loped through copolymeri&ation of tall oil samples with indene- coumarone. Finally the film properties of these end-products thus obtained were investigated. The experimental results showed that these new products could be used succesfully in the field of organic surface coating. At first, general chracteristies and composition of crude tall oil samples were determined. Results thus obta ined showed that Dalaman and Çaycuma tall oils contain about 73% and 55% resin acids, about 20% and 30%, fatty acids and 7% and 13% unsaponif iable matter, respectively. Tall oils of turkish origine are comparatively richer in resin acids and poorer in fatty acids than the other tall oils originating from some other countries listed in Table 1.5 (p. 11). The identification of the fatty and resin acids of both tall oil samples were carried out mainly by theIX aid of a Variati 2100 type gas chromatographic set. Quantita tive gas chromatographic evaluations of the fatty and resin acids contents are summarised in Tables 2.3 and 2.4 (p. 27 and 28, respectively). As seen from Table 2.5 (p. 28), the fatty acid composition of Dalaman and Çaycuma tall oils are respec tively as follows: 17,07% and 6,4% saturated; 56,3% and 46,9% monounsaturated; 25% and 39,9% diunsaturated and 1,7% and 7,2% triunsaturated. These fractions contain also 7,7% and 16,1% conjugated fatty acids, respectively. In order to obtain a light-colored and odorless refined tall oil, acid refining process was directly applied for Çaycuma crude tall oil. On the other hand, the similar raw material, xvhich was obtained from Dalaman Pulp and Paper Plant as a sulphate soap, has been refined first and after subsequent acidulation the final rafinate has been thus obta ined. For the preparation of indene-coumarone of tech nical purity, a definite refining process also was applied to the tar-oil fraction (b.p. 150-230 °C) which was obtained from Karabük coal-tar distillation stills. The tar-oil distillate showing a boiling range of 150-230 °C, was washed first with caustic soda to remove the tar acids (phenols) and then with dilute sulphuric acid to remove tar bases such as pyridine etc. This fraction was purified in a further stage by cooling and crystallisation in order to remove the dissolved naphthalene and the refined oil named as `neutral oil` was thus obtained.In order to prepare indene-coumarone of techni cal purity in a high yield, several distillation treatments on this neutral oil were carried out at 15 mm Hg and atmosphe ric pressure under different conditions i As a result of these experiments, optimal distillation pressure and temperature range were found to be 15 mm Hg and 37-79 °C. This fraction of technically pure neutral oil quality consisted of approxi mately 80% polymerizable monomers of indene-coumarone and was used in all experiments of this investigation. Kaufmann and Briinning (85) have already shown that a copolymerization Reaction takes place at 280 °C between indene and some vegetable oils such as linseed, cottonseed and soybean oils. They have also proven that first an isome- rization of the triglycerides' double bonds occurred at high temperature, then an addition proceeded between indene and these conjugated double bonds in accordance with the Diels- Alder reaction scheme. In this investigation it is shown that, the co- polymerization reaction between tall oil and indene-coumarone could begin readily at a lower temperatures than 280 C. This can be just explained with the in some degree conjugated natu re of tall oil. Taking in consideration this fact, experiments on the copolymerization of the above cited materials were con ducted at large intervals of temperatures and heating periods. According to the experimental results, 240 °C and 16 hours were determined as an optimal temperature and heating time. In view of investigating the effect of the components* ratioXI (tall oil to indene-coumarone) on the composition of the resulting copolymerisate, another set of experiments were conducted at these optimal conditions. Consequently the appropriate ratio of tall oil to indene-coumarone was found to be 73:27 for Dalaman and 74:26 for Çaycuma samples res pectively, x Indene-coumarone copolymerisates of both tall oil samples preparatively obtained by applying the optimal conditions and the ratio of components mentioned above; and esters of these copolymerisates with ethyleneglycol, glyce rol and pentaerythritol were subsequently prepared. Finally, in order to obtain the corresponding urethanes these penta erythritol esters were also reacted with TDI (toluen diiso- cyanate consisting of 80% of 2,4-, and 20% of 2,6- isomers). In order to compare the final polymers mention ed above with some standard formulation of organic surface coatings, the following tall oil and vegetable oil based ve hicles have been prepared: boiled linseed oil, boiled linseed: tung oil (90:10) mixture, linseed oil modified long oil alkyd resin, the indene-coumarone copolymerisates of both linseed and sunflower oils, the pentaerythritol esters of both tall oil samples and their corresponding urethanes. At the last stage of this study, film proper ties of all the final samples were investigated.XII Evaluation of data concerning the film proper ties indicated that all the copolymerisate based products showed superior alkali-, and water resistance and excellent water absorbency in comparison with the oil based products. But their adhesion and bending properties were to a minor extent not as good as the oil based products. Some further attempts were made for preventing the bending brittleness of these new products and a great improvement in the adhesion and bending ability of the final product was experimentally observed when the indene-coumarone content of the copolymerisate was increased. As a conclusion, the film properties of copoly merisate based products showed that these could be used suc- cesfully in the field of organic surface coating. There is a steadly increasing need for such low-cost and durable organic surface coating based on indus trial by-products, particularly in Turkey, and it is believed that surface coatings formulated with indene-coumarone copoly- merisates of tall oil will satisfactorily fill this need to some extent. This investigation and tests on these new pro ducts may much contribute toward justifying this thesis.