Technology organic and inorganic substances UDC 665.765-404.9.001.5.038.5 Визначені антиокиснювальні та протикорозі- йні властивості в оливах продуктів конденсації DOI: 10.15587/1729-4061.2016.71267 алкілфенолів з параформом і полімером тіоціа- нової кислоти. Досліджено продукти конденсації ALKYLPHENOL 5-аміно-1,2,4-дитіазол-3-тіону (ксантангідриду) з 2,6-ди-трет-бутилфенолом і параформом. Зокрема, DERIVATIVES OF у розчині льодяної оцтової кислоти утворюється суміш продуктів, у яких співвідношення фрагментів THE POLYMER OF ксантангідриду і 2,6-ди-трет-бутилфенолу стано- вить 1:1 та 1:3. На основі хімічних і спектральних THIOCYANIC ACID даних зроблено припущення щодо будови речовин. Встановлено, що найлегше розчиняються в оливах AND 5-AMINO-1,2,4- продукти з високим умістом 2,6-ди-трет-бутилфе- нольних залишків DITHIAZOLE-3-THIONE Ключові слова: ксантангідрид, 2,6-ди-трет- бутилфенол, параформ, основи Манніха, беззоль- AS AN EFFECTIVE ні інгібітори окиснення, термоокисна стабіль- ність, корозія, антиокиснювач, тіоціанова кисло- ADDITIVES TO FUELS та, паливно-мастильні матеріали AND LUBRICANTS Определены антиокислительные и антикорро- зионные свойства в маслах продуктов конденсации O. Vasylkevych алкилфенолов с параформом и полимером тиоциа- Candidate of Chemistry, Associate Professor* новой кислоты. Исследованы продукты конденса- Е-mail: [email protected] ции 5-амино-1,2,4-дитиазол-3-тиона (ксантанги- O. Kofanova дрида) с 2,6-ди-трет-бутилфенолом и параформом. Doctor of pedagogical sciences, В частности, в растворе ледяной уксусной кислоты Candidate of Chemistry, Professor** образуется смесь продуктов, в которых соотно- Е-mail: [email protected] шение фрагментов ксантангидрида и 2,6-ди-трет- K. Tkachuk бутилфенола составляет 1:1 и 1:3. Основываясь Doctor of technical sciences, Professor** на химических и спектральных данных, высказано Е-mail: [email protected] предположение о строении веществ. Установлено, O. Kofanov что лучше всего в маслах растворяются продукты Postgraduate Student** с высоким содержанием 2,6-ди-трет-бутилфеноль- Е-mail: [email protected] ных остатков Ключевые слова: ксантангидрид, 2,6-ди-трет- *Department of Organic Chemistry and бутилфенол, параформ, основания Манниха, беззо- Technology of Organic Compounds*** льные ингибиторы окисления, термоокислительная **Department of environmental engineering*** стабильность, коррозия, антиокислитель, тиоци- ***National Technical University of Ukraine ановая кислота, топливно-смазочные материалы "Kyiv Polytechnic Institute" Peremogy ave., 37, Kyiv, Ukraine, 03056 1. Introduction cessfully used in this sphere. Each of these types of additives has some advantages as well as disadvantages. Antioxidants are one of the most important components Hindered phenols and secondary aromatic amines have among the additives to the fuels and lubricants. For example, an advantage because they are almost ashless additives. dithiophosphates and dithiocarbonates of metals (mainly – But they do not protect metal surface from corrosion. zinc dithiophosphate), secondary aromatic amines (N-phe- Aromatic amines in comparison with the hindered phe- nyl-α- and β-naphthylamines, N,N-dioctyldiphenylamine), nols are more toxic and, in addition, they are able to color hindered alkylphenols, etc. have obtained the broadest lubricants during the oxidation process. At the relatively practical application in the lubricants. Alkylsalicylates of low temperatures, 4-methyl-2,6-di-tert-Butylphenol (Ion- the alkaline-earth metals also have good antioxidative and ol) is one of the most effective hindered alkylphenols. It is anticorrosive properties in the fuels and lubricants. a unique component of the additives in the breadth of its Extensive synthetic investigations in the 1930s have led to application because in the second half of the 20th century the creation of the antioxidants that are valuable even today. it has been already used in the global market by more than It was found that hindered alkylphenols are the most effective 70 trademarks. However, Ionol has a high volatility that is among phenolic antioxidants. All contemporary chemistry of a significant disadvantage. the phenolic antioxidants is based on them. Even today vari- Thus, synthesis of the effective ashless high-temperature ous derivatives of the 2- or 2,6-di-tert-Butylphenols are suc- additives to the fuels and lubricants is urgent today. 45 © O. Vasylkevych, O. Kofanova, K. Tkachuk, O. Kofanov, 2016 Eastern-European Journal of Enterprise Technologies ISSN 1729-3774 3/6 ( 81 ) 2016 2. Analysis of the literature sources and problem statement tally safe reagents for the synthesis of the compounds that have similar structure to the tris-(alkyl-oxybenzylthio)-triazines One of the most common classes of the antioxidants are and provide high antioxidative activity, availability of the phenol derivatives [1] that may also contain alkyl groups raw materials, simplicity of the synthesis, thermal stability, that screen hydroxyl group, thereby increasing the oxidant low volatility, and multifunctionality. capacity of additives. However, their usage is limited because One of the available raw materials for the synthesis of the of the insufficient thermal stability. For example, adding of additives to the lubricants is ammonium thiocyanate that 0.5 % of the di-tert-Butylhydroquinone significantly im- during fusion with the hydrosulfates of the alkaline metals proves the stability of the biodiesel, but, as it has been shown or ammonium forms the mixture of the TTCA (~10 %) and by the analysis of the oxidation induction period by the the thiocyanic acid polymer (N≡C–SH)n (~60 %) [15]; and ASTM D-6751 method, the necessary degree of the stability with the sulfuric acid – 5-amino-1,2,4-dithiazole-3-thione has not been achieved [2]. Zinc dithiophosphates have quite (Xanthane Hydride) [16]. high antioxidant effectiveness [3, 4]. However, the usage of Earlier it was reported [17, 18], that the thiocyanic acid these antioxidants in the fuels is limited because they are polymer and 5-amino-1,2,4-dithiazole-3-thione react with ashy. In addition, they are not enough thermally stable and paraformaldehyde and alkylphenols and form products that reduce the colloidal stability of the lubricants. show multifunctional properties in the oils. Consequently, Alkylsalicylate derivatives of the metals are more sta- the usage of the available raw material – ammonium thio- ble [5], but they also belong to the ashy additives. Decom- cyanate – for the synthesis of the new perspective additives posing at the high temperatures, for example, in the area of to fuels and lubricants is urgent and requires more detailed the engine piston rings while being used in the motor oils study of their functional properties and structure. they participate in the formation of the deposits. Ash is also an obstacle for the nanomaterials usage in the fuels and lu- bricants, in particular, zeolites, which also have the ability to 3. Research aim and tasks increase resistance of hydrocarbons to oxidation [6]. Hindered alkylphenol Mannich bases also deserve atten- The aim of the investigation is to obtain highly efficient t i o n [ 7–9]. In particular, N-benzyl-N,N-bis-(3,5-di-tert-Butyl- and thermally stable additives to the fuels and lubricants. 4-hydroxybenzyl)-amine is an effective inhibitor of the com- For ensuring reliable operation of the mechanisms, these plex lithium lubricants oxidation [8]. It is reasonable to use products have to be ashless, maintain antioxidative proper- it in the high-temperature lubricants. Alkylphenol Mannich ties at the temperatures above 200 oC and contain heteroat- bases are actively researched and patented not only as com- oms and cyclic fragments that are able to provide multifunc- ponents of the lubricants but also as additives to the fuels tional properties in the oils and motor fuels. [10]. The usage of the Mannich reaction for the industrial To achieve the aim of the research, the following tasks products synthesis is considered as perspective because it is were set: rather simple and technically “convenient” and can be easily – synthesis of the alkylphenol derivatives of the thiocy- implemented in practice. It is also characterized by minimal anic acid polymer and 5-amino-1,2,4-dithiazole-3-thione waste formation. (Xanthane Hydride); Derivatives of the 1,3,5-triazine are also interesting – determination of the functional properties of the syn- additives among the high-temperature antioxidants of the thesized additives in the oils; organic compounds [11, 12]. 1,3,5-Tris-(3,5-di-tert-Butyl-4- – optimization of the method of the Xanthane Hydride hydroxybenzyl)-isocyanurate (trade marks Good-Rite 3114, synthesis and structure determination of the products of Irganox 3114) is thermally stable up to 300 oC (it loses 7 % of its condensation with paraformaldehyde and 2,6-di-tert- the weight) and tris-(3,5-di-tert-Butyl-4-hydroxybenzylthio)- Butylphenol(2,6-DTB). triazine (TTS) loses 7.5 % of the weight up to 250 oC. Anti- oxidant activity of the hindered alkylphenol derivatives of the sym-triazine depends also on the origin of the groups that 4. The results of the research of the properties of the connect triazine ring with the phenolic fragment. The sub- additives to the fuels and lubricants and their discussion stances in which 1,3,5-triazine is connected with the hindered alkylphenol by sulfur, i. e. compounds of the TTS-type, have the 4.. 1 Alkylphenol derivatives of the thiocyanic acid highest antioxidant activity [11]. polymer Trithiocyanuric acid (TTCA) is a good reagent for Thiocyanic acid polymer (–С(SH)=N–C(SH)= the synthesis of the sulfuric alkylphenol derivatives of the =N–C(SH)=N–)n, that is synthesized by the reaction of the sym-triazine. Synthesis of the compounds based on the ammonium thiocyanate with the anhydrous NaHSO4 [15], TTCA with paraformaldehyde and alkylphenols is quite can be considered as the linear analogue of the TTCA. The simple. However, there are some problems during TTCA molecular mass of the polymer, determined by the ebullio- synthesis from 2,4,6-trichlorotriazine by the reaction with scopic method in the pyridine, is ~6000. thiocarbamide or Na2S and NaHS [13]. Thiocyanic acid polymer was synthesized in this way.