CS250026B1 - A method for producing a synthetic lubricant and / or component - Google Patents

Abstract

The synthetic lubricant or lubricant component is produced by esterification, transesterification, or polyesterification at a temperature of 90 to 280 °C in the presence of esterification and polyesterification catalysts, whereby 100 parts by weight of the oxygenated organic by-product (density at 20 °C = 1010 to 1115 kilograms . oi'3; acid number 150 to 300 milligrams KOH/g; saponification number 250 to 480 mg KOH/g; bromine number = 18 to 55 g Br/100 g; OH = 3 to 8% by weight), isolated as a residue from the digester of the hydrolysis column after separation of part of the water, from the production of cyclohexanol and/or cyclohexanone by oxidation of cyclohexane, is condensed and/or polycondensed with 5 to 60 parts by weight of with parts of at least one pentavalent to hexavalent alcohol, optionally in a mixture with divalent alcohol. The product obtained is physically and chemically modified. It is particularly suitable for lubricating chain gears, motion screws, toothed bars and steel ropes.

Description

The invention relates to a process for the production of a synthetic lubricant and / or lubricant component, in particular high viscosity lubricating oils and lubricants based on traditional as well as novel starting, low-value petrochemical raw materials.

In addition to modern petroleum oils, the importance of synthetic oils and lubricants is increasingly becoming increasingly important not only in terms of quantity but also in their reliable function under normal and particularly extreme conditions. These include mainly polyalkylene glycols, respectively. polyalkylethers, oligomers and low molecular weight polymers of alkenes, acyl aromates, polyphenylethers, chlorinated and especially fluorinated hydrocarbons, polysiloxanes, alkyl esters, as well as aryl esters of trihydrogenphosphoric acid, alkyl esters of monocarboxylic aliphatic acids (Štěpina V., Veselý V. ).

Of the alkyl esters of the monocarboxylic acids, the C5-C10 monocarboxylic acid esters and polyols, in particular the neoalkyl polyols, and in particular trimethylolproipane, ipentaerythriol and dipentaerythritol, are of particular importance. Significant monoesters include esters prepared from 2-ethylhexanoic acid and heptanol, as well as 2-ethylhexanol and isooctadecanol. Then from isodecanoic acid and n-hexadecanol, heptanoic acid and isononanol and isotridecanol.

Diester oils include, in particular, oil prepared from dipropylene glycol and n-nonanoic acid and pelargonic acid, 1,6-hexanediol with acids:

2-ethylhexane, n-nonanoic, isodecane and isotridecane.

Pentaerythritol esters of acids are known from the tetraol esters:

n-heptane, n-octane, n decane, isodecane and isostearic.

However, there is a shortage of limited raw material resources, which also hinders the wider application of ester and polyester oils. A similar situation applies to alkyl esters of dicarboxylic aliphatic acids (Hickeman, K. C., Sanford, C. R., Rev. Sci Instr. 1, 140 (1930)); Nikeron E. M. et al. teach. pimple. Vsesojuz. naučno-issled. inst. pererab. Nepti 42, 66 (1982); Imporato L. et al., SAE Preprint 740 118 (1973); Rumpf Κ. K .: Mineraloltechnik 16, 11 (1971); Stech W .: Mineraloltechnik 17, 10 (1972), or diester oils.

Also noteworthy is the (art. No. PV 5086-84) method of producing a synthetic lubricant from an oxygen-containing by-product from the production of cylclohexanone and / or cylclohexanol, and alcohol, diols to tetraols, but not only water is removed from the by-product, but also an organic fraction with a boiling point of 100 to 200 ° C, which technically complicates production and increases energy and raw material consumption.

On the other hand, the method for producing a synthetic lubricant and / or a component of lubricants based on acid, catalyzed organic compounds, esterification, transesterification and / or polyesterification at a temperature of 90 to 280 ° C, as a rule with the esterification and / or polyesterification catalyst (s). 100 wt. parts of the oxygen by-product organic product isolated as a distillation residue from the hydrolysis column after separation of at least a portion of the water from the production of cyclohexanol and / or cyclohexanone by oxidation of cyclohexane, having a density at 20 ° C of 1,010 to 1,115 kg. m ~ ³ , acid number 150 to 300 milligrams KOH / g, saponification number 250 to 480 mg KOH / g, bromine number 18 to 55 g óm2 / 100 g, hydroxyl group content 3 to 8 wt. % is condensed and / or polycondensed with 5 to 60 wt. parts of a pentavalent and / or hexavalent alcohol.

The advantage of a process for making .According to the invention is the use of technical hitherto low ¹ recovered a by-product from the production of cyclohexanone and / or cyclohexanol, usually isolated as a residue from the digester hydrolysis column after separation of at least part of the water, the production of quality lubricants, oil seal, especially for © formed by transfers.

Further, the flexibility of production by the application of a pentavalent to hexavalent alcohols, if desired, in admixture with dihydric to quaternary alcohols, depending on the intended use of the lubricant or lubricant component as well as the raw material and technical availability of the polyhydric alcohols.

The oxygenated organic by-product of cyclohexanol and / or cyclohexanone production by oxidation of cyclohexane, isolated usually as an organic residue from the reboiler of the hydrolysis column after separation of a substantial part of water (e.g. column D 110j) has a density of 20 ^and C ^-3 ; water content 4 to 10% by weight; acid number 150 to 300 mig KOH / g; saponification number 250 to 480 mg KOH / g; bromine number 18 to 55 g Br / 100 g; hydroxyl groups content 3 to 8% It consists of a mixture of monocarboxylic and dicarboxylic acids, hydroxy and keto acids, their cyclohexyl esters and diesters.

Furthermore, lactones are present in monomeric form, but also dimers and polymers. Monocarboxylic acids (butyric, caproic, valeric acid, dicarboxylic acids (succinic, glutaric, adipic) and hydroxylic acids (delta-hyd5 β) were identified.

δ ο roxybutyric acid, hydroxyvaleric and hydroxycaproic acid). Then esters of said and other carbon acids (cyclohexyl valerate, cyclohexyl caproate, dicyclohexyl glutarate, cyclohexyl adipane).

In addition, they contain admixtures of cobalt, iron, nickel, titanium and zinc compounds. However, the admixture of the metal compounds is usually freed by scrubbing with the co-treatment of strong mineral acids, optionally with the co-treatment of oxidizing agents, chelating agents and ion exchangers.

The bivalent alcohol according to the invention is understood in particular to mean:

monoethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, diethanolamine,

1,3- butanediol,

1,4- butanediol,

1,6-hexanediol, diols Ce, diols C12.

By trivalent alcohol is meant primarily glycerol, trimethylolpropane, triethanolamine, but also ethoxylation products as well as propoxylation of glycerol-and trimethylolpropane, further products of the ethylene oxide and / or propylene oxide ipolyadiation to the above and other technically available trivalent alcohols.

Of the tetravalent to hexavalent alcohols, the most important are pentaerythritol, xylitol, dipentaerythritol, reduced sugars, ethylene oxide addition and polyaddition products, as well as propylene oxide to polyhydric alcohols, by-products from the production of trivalent to hexavalent alcohols, e.g. from the production of trimethylolpropane as well as pentaerythritol and dipentaerythritol, the so-called. syrups.

Further, the products of their addition and polyaddition with ethylene oxide as well as propylene oxide, also products of copolyaddition of ethylene oxide with propylene oxide into trivalent to hexavalent alcohols.

To accelerate esterification, respectively. The esterification and polyesterification catalysts which are known to be suitable are, for example, the following esterification and polyesterification catalysts, such as:

mineral acids, organic sulfacids, cations, tin, titanium, zirconium, manganese, germanium and the like compounds.

In many cases, it is appropriate to combine esterification and ipolyesterification catalysts, even with predominantly p-reesterification catalysts, such as e.g. manganese, antimony, molybdenum-and lead compounds.

The degree of cross-linking and viscosity of the final product determines the type and amount of polyhydric alcohol used, or the mixture of polyhydric alcohols, respectively. the ratio of the individual components of the reaction mixture to esterification, pre-esterification, and polyeserification.

To facilitate generally high viscosity and / or solid products, these are prepared, particularly in an environment where it is possible to heat the lubricant from safety or application lines by adding non-flammable, easily volatile solvents.

In some cases, a mixture of viscous and solid products is used, containing suitable additives, e.g. Ik-oloid graphite. Depending on the application of the lubricant and / or component, it is advisable to add lubricating additives to the lubricants, such as antifoams, emulsifiers, anticorrosive additives, antioxidants and the like.

The products obtained are particularly suitable for the lubrication of chain gears, articulated and gravity, furthermore for the lubrication of movement cabinets and toothed racks, steel ropes, because they have not only a high viscosity but also a good natural adhesion to the rope surface. Moreover, they do not flow even at higher outside temperatures and are sufficiently elastic even in winter.

The process of the invention can take place in particular discontinuously, but may be implemented HO- and semi-continuously, typically ipoužitia liquid or gaseous ,, · ^scavengers': water, elevated, especially the atmospheric .or vacuo.

Further data on the production method of the invention as well as other advantages are apparent from the examples.

Example 1

Weigh 2,000 g of organic residue from the hydrolysis column after separation of part of the cyclohexanone production by catalytic oxidation of cylclohexane to a 4-necked flask of 4 dm ³ equipped with a stirrer, contact thermometer, inert gas inlet, adapter, condenser and condenser. This organic residue (from the DX 110 column) has the following characteristics:

a tan to dark brown liquid; the dynamic viscosity at 20 ^D C - 268.9 MPa. .with;

density - at 20 ° C - 1106 kg. m ³ ;

water content = 6.9% by weight;

acid number - 236.3 mg KOH / g;

saponification number = 412.8 mg KOH / g;

bromine number = 23.1 g Br / 100 g;

hydroxyl group content = 4.7 wt.

Next, 280 g of dipentaerythritol, 20 g of polyprcipoxylated trimethylolpropane and 5 g of tetrabutyl titanate are added as esterification, pre-esterification and esterification poles. The reaction is carried out at a temperature of 200 ° C using CO g of xylene as. water carrier. The product obtained after separation of the fractions under reduced pressure has an acid number of 0.9 mg KOH / g; saponification number 360.2 mg KOH / g and dynamic viscosity at 50 ° C 6 Si20 mPa. with. The product has a very good adhesion to the steel sheet and, at a temperature of -20 ° C, adheres well to the surface, it is particularly suitable for the open gears.

Example 2

Weigh 200 g of the by-product organic oxygen product - the distillation residue from the hydrolyzing Icol column / cyclohexanone production / into a three-necked 500 cm ^{3 3} -necked flask with stirrer, contact thermometer, inert gas inlet, filler, cooler and distillate collection flask. or cyclohexanol, characterized in Example 1, further 30 g of xylitol with a melting point of 92-94 ° C, 15 g of ethylene glycol, 30 g of xylene, 0.8 g of p-toluenesulfonic acid. The reaction is carried out at 120 to 160 ° C for 26 h. The product obtained after separation of the solvent by distillation under reduced pressure, neutralization and drying of the product has an acid number of 0.6 mg KOH / g, a kinematic viscosity of 2,850 m ² . s ^-1 and is after aiditivation

0.5 wt. 2-tert-butyl-4-cumylphenol as an effective antioxidant as a lubricant suitable for open gears.

Example 3

Weigh 2,000 g of the by-product of the oxygen-by-product distillation residue of the hydrolysis column from the cyclohexanone production into a three-necked 4 dm · ⁵ esterification flask equipped with stirrer, contact thermometer, inert gas inlet, cooler and distillate collection flask. or cyclohexanol, characterized in Example 1, 200 g of 85.4% pure dipentaerythritol, containing in addition 14.6% of pentaerythritol, 50 g of ethylene glycol and 4.5 g of tetrabutyl titanate as catalyst.

The reaction is carried out at 200 ° C for 26 h, while the reaction mixture is purged with nitrogen, separating the reaction water - and a small amount of low boiling. The product has a cinematic viscosity of 380 mm ² at 100 ° C. ^s1 and is suitable as a lubricant for open gears. When the product was cooled to 50 DEG C. in the reaction flask, 10% trichlorethylene, 0.2% by weight was added to the viscous product to facilitate collection and application. magnesium arylalkyl sulfonate, 0.15 percent phenolizine, 0.3 wt. N, N'-diphenyl-p-phenylenediamine, 0.1% N, N'-bis-salicylidene-1,2 diamino propane, 0.2% w / w; zinc dialkyldithiophosphate and 0.05% anthranilic acid.

Claims (3)

1. A process for the production of a synthetic lubricant and / or a component of oxygen-based organic compound lubricants by esterification, esterification and / or polyesterification at a temperature of from 90 to 280 [ ^deg .] C., generally with the aid of an esterification catalyst and / or polyesterification catalyst; characterized in that 100 wt. oxygen-containing organic components by-product recovered as the distillation residue of the reboiler of the column after separation of the hydrolysis of at least part of the water from the production of cyclohexanol and / / or cyclohexanone oxidáclou cyclohexane, a density at 20 C ^and 1010-1115 kg. . m ³ , acid number 150 to 300 mg KOH / g, saponification number 250 to 480 mg KOH / g, bromine number 18 to 55 g Br / 100 g, hydroxyl group content of 3 to 8% by weight are condensed and / or polycondensed s 5 V V Μ A L E Z U to 60 wt. parts of pungent and / or six + strong alcohol. 2. A process according to claim 1, wherein 100 wt. parts of the oxygen by-product organic product are condensed with 5 to 60 wt. parts of a bivalent and / or bivalent hexavalent alcohol, preferably containing primary hydroxyl groups, and used in admixture with 1 to CO% of at least one two- to four-valent alcohol. 3. Process according to claim 1 or 2, characterized in that the viscous to solid product obtained is generally physically and / or chemically treated, such as by distillation of the lighter fractions under reduced pressure, extraction, dilution by addition of non-flammable solvents, additivation of antioxidants. other customary flavor additives.