Synthesis of modified ketonic resins with functional amine compounds

Ketonic resins are obtained by the reaction of ketones which contains α-hydrogen and aldehydes. Most common ketonic resins are cyclohexanone-formaldehyde resins. If we compare with the other ketonic resins cyclohexanone-formaldehyde resins show low molecular weight and they are not used as single mostly they are mixed with other polymers and can be applied as additive for industry of coating, dope, ink, paper. Numerous reports about aliphatic and alicyclic ketone-formaldehyde resins exist for many commodity applications like paints, foam, adhesives, and molding materials. Cyclohexanone-formaldehyde resin (CFR) has good utility because it has excellent glossy and transparent properties. Due to their high compatibility and solubility with wide range of film formers, resins (CFR) play a key role in the field of coatings (paints, inks, varnish, lacquers and light stabilizers as a blend for the improvement of coating properties and as an adhesive in multilayered laminated sheets. Synthesis of ketonic resin containing copolymers has been extensively studied since the ketonic resin segments improves adhesive, solubility, gloss, and light stability of parent polymers. In a recent communication, we briefly reported the synthesis of well-defined acetophenoneformaldehyde resin containing ABA type block copolymers by atom transfer radical polymerization (ATRP).Ketones containing a-hydrogens react with formaldehyde in alkaline solution to give thermoplastic ketone-formaldehyde resins. Their molecular weight is in the range of1000. In the coating industry, these resins are used as additives to modify the properties of high molecular weight film formers.Recently, cyclohexanone-formaldehyde resins are modified in situ and after the polymerization with different conditions and different modifiers to increase the chemical functionality of obtained polymers. In situ modification of cyclohexanone-formaldehyde resin (CF-R) has been studied by base catalyst condensation previously. The modifier compounds were phenols,bisphenols, melamine, p-toluenesulphonamide (Kızılcan et al., 1993; Kızılcan and Akar, 1996) salicylic acid, o-cresol, p-cresol, citric acid (Kızılcan and Akar, 1999), polydimethylsiloxane (Kızılcan and Akar, 2005).In this study cyclohexanone-formaldehyde polymerizations are made in basic media and temperature catalysis. In different mole ratios, with in situ or after modification reaction of cyclohexanone with monoethanolamine, cyclourea and glycolamine compounds via α-hydrogens. If we compare the modified and unmodified cyclohexanone-formaldehyde resins, they show different properties from each other, observed different physical properties and chemical structures in different ratios, observed changes identified by spectroscopic methods. Modifier compounds are usually added to the reaction flask either at the beginning of polymer preparation or the later stage of resin formation, depending on their reactivity. The proper choice of modifier compounds usually results in satisfactory physical properties, such as solubility, melting point, and chemical reactivities.Obtained resins' NMR, FTIR and melting point analyses show the occurring changes in structures. With these researches, the possible structure forms are identified. These structures are approved and drawn by the stated analysismethods.The change of the materials we used for the modifications of Cyclohexanone-formaldehyde resins have very variable properties that we obtained the results from the spectroscopic methods. Glycolamine and monoethanolamin make polymers more liquid than the other types of the polymer addition characteristics.Some of the obtained polymer can be soluable at the water some of them are not soluable in any solution and some of the polymers have low melting point compare to other polymeric blends. But for the end of the polymer product all of them show nonflammability than the cyclohexanone-formaldehyde resins that could be achieve more potential than cyclohexanone-formaldehyde resins.Because of this reasons and the results showing us the importance of the additive usage in cyclohexanone-formaldehyde resins. That leads us to very different aspect and has more potential than cyclohexanone-formaldehyde resins.For this purpose glycolamin, monoethaolamin and alendronic acid and theirs cyclourea compound studied and studies leads us to study in different ratios of the addition to the cyclohexanone-formaldehyde resin compotions. %20, %10 and %40 studied in the purpose of determining the effect of different ratios for the functionalization of the formaldehyde-cyclohexanone resin compositions. Determined that the %20 addition of the material as mass ratio of the additive has optimum effects on polymer.In the studies of %10 a few changes in the polymeric structure has seen and the chemical and physical properties didn't change at all. In the %40 studies polymeric structure changed a lot and the cyclohexanon-formaldehyde resin compositions cyclohexanon-formaldehyde characteristics are vanished by the additive used in the polymeric composition.The difficulties of the study were the solubility and the low molecular weight of the obtained polymers. Because polymeric structures can not be measured by the Gel Permission Chromatography (GPC) techniques. Values that we obtaine from the polymeric structures are less than the value of GPC can measure. Besides other tecniques to measure the structure are not suitable for the polymeric compositions.On the other hand obtained polymeric structures has very interesting solubility in organic solvent such as dichloromethane and Toluene. In the normal characteristics of cyclohexanone-formaldehyde resins, they are soluable in this organic solvents but some of the polymeric composition we obtained from the studies don't solve neither DCM nor Toluene. But some of the polymeric structure we achieved to solve them in water solvents.For the reason of some of the polymeric structure solve in the water separating the Formaldehyde from the polymeric structure is another struggle to solve while studying these compound. At the normal process of cyclohexanone-formaldehyde formaldehyde can be separated by the adding water on the solution we obtained in the final solution, in this studies we could not use water because of the solubility of the polymeric structure. For this purpose tried to evaporate in the vacuum evaporator and driers.For the purpose of usage in industrial area, synthesized polymers are used in polymer has a common use in industrial area; Polyurethane. Chemical and physical property changes in obtained polyurethanes with these resins will be determined, and different characteristics with different obtained additive usages will be studied.Against all odds nonflammability of the polymeric structures are obtained and can be tested in the future studies of this thesis project.For the purpose nonflammability will be determined by flammability test of modified polyurethanes with the obtained cyclourea compounds which are increased nitrogen amount in the polymer.