DE969479C - lubricant - Google Patents

Description

Lubricants It has been suggested to use synthetic oils, in particular certain esters of dibasic aliphatic acids, as oil components for fats, Use engine oils, high pressure lubricants and similar substances. Albeit lubricant on the basis of these esters excellent lubrication properties as well as an outstanding one Many of these compounds will behave at high and low temperatures easily hydrolyzed. Also, the area of raw materials available is pretty limited. Given the rapidly increasing demand for synthetic lubricating oils In many areas, therefore, a broadening of the raw material base is very desirable. Ether have not previously been used as synthetic lubricating oils because they are at low levels Pour points also have low flash points, while the ethers have high flash points also have high pour points. For example, dicetyl ether, (C18H33) 20, has a melting point of 55 ° and didodecyl ether, (C "Hzs) ZO, one of 32.2 °. Such ethers are accessible from the corresponding alcohols, which in turn are from natural Fats and oils can be obtained by various chemical methods. These Ethers have straight chains and are highly inert, which makes them like aliphatic Hydrocarbons are suitable for lubrication purposes. They are, however, owing to them high Melting points little if any as a lubricant for Crank tubs can be used. On the other hand, ethers, which have high flash points, would be good lubricity and combine viscosity properties with a low pour point, extraordinary valuable lubricating oils.

It has now been found that in the manufacture of lubricating oils and -fats low-boiling mineral oil fractions and synthetic oils of the types described Kind can be replaced by branched-chain ethers, which are the composition R-O-R 'where R and / or R' have branched chain hydrocarbon radicals of at least 8 carbon atoms are. These ethers have excellent lubricating properties and connect relatively high boiling points with desirable low pouring points, high ones Flash points, low viscosity-temperature coefficient and high chemical Resistance. Even if this group of connections in their full breadth can be used for synthetic lubricants are those members of the group which pour points below -7 °, advantageously below -: z6 ', and flash points above i49 °, ideally as lubricating oil bases in general and for production particularly suitable for high and low temperature greases.

According to the preferred embodiment of the invention, those used have Ether-branched-chain hydrocarbon radicals R and R ', each of which has at least 8 Contains carbon atoms. These compounds can be made up of branched monovalent or polyvalent ones Alcohols with at least 8 carbon atoms through the usual esterification reactions with concentrated sulfuric acid or sulfonic acids. Examples of such Ethers are those from 6-methyli-heptanol, 2-n-propyl-i-pentanol, 3-n-propyl-i-hexanol, 2,2-Dimethyl-i-octanol, io, io-dimethyl-i-undecanol, 3-isopropyl-i-heptanol derived Links. Mixed straight and branched chain ethers, in which R is a branched one Remainder and R 'is a straight-chain residue, you can z. B. by reaction of a branched chain Prepare alcohol R 0 H with Na 0 H, whereby the alcoholate formed R O Na with chlorinated Wax or the like can be implemented to form the desired ether. The reaction between the alcohol and NaOH takes place at temperatures of about 77 to 177 ° in the presence an entrainer, such as a hydrocarbon or excess alcohol, which is suitable for removing the water of reaction. The reaction v-, ischen dem Alcoholate and the chlorinated wax take place at temperatures of about 66 to 2o4 °.

It was also found that consistently good results are always achieved when using a group of ethers derived from the product or by-product alcohols the known oxo synthesis are produced.

Even if the exact composition of all these alcohols is not known is, it is certain that it is a mixture of primary alcohols, at least a substantial portion of which contain branched chains. The alcoholic Top product consists of a mixture of such alcohols with an average of 1 carbon atom more than the starting olefin had. For the purposes of the present invention are oxo alcohol ethers, the branched-chain hydrocarbon radicals with at least 8, advantageously containing 10 to 20 carbon atoms, preferably used.

Ethers with excellent properties can be obtained from oxo alcohols are, in turn, by treating polymers and copolymers of C3 and C4 monoolefins are formed in a known manner in the presence of oxonation contacts.

Some of the basic properties of ethers made from oxo alcohols are compared in the table below with those of known mineral and synthetic lubricating oils. Manufactured by flow-flame viscosity, cst Lubricant Oxosynthesis from point point at. at. at 0 C ° C 98.9 ° 37.8 40.0 ' Di-C8 oxoadipate C, copolymer <-59 204 2.81 9.84 1040 made of butylene and Propylene. Di-C "6 oxoadipate C9 polypropylene <- 59 241 4.70 2o, 83 2950 Lubricating oil based complex ester -51 . 243 io, i 52.0 31000 Extracted Mid-Continent Mineral oil -21 210 4.99 29.8 solid Ether of the C13 oxo alcohol Clä polypropylene <-54 193 3.29 14.6 6448 Ether of Cl oxo alcohol C15 polypropylene - 48 216 5.87 43.4 io ooo The table above shows that the new oxoethers according to the invention perform very well when compared with synthetic lubricants and mineral oils.

The flash point and viscosity are in the range desired for use at low temperatures. The carbon and hydrogen content of the ether obtained from the C "alcohol was determined and a good agreement between the values found and the calculated values was established Found Calculated Carbon, l) / o. . . . . . . . . ; 82.8 82.4 Hydrogen, ° / o. . . . . . . . . i4.3 i4.2 The oxoethers were prepared according to the methods described below. No protection is claimed for the production process of the ethers.

Method i The ether of the C13 oxo alcohol fell in a yield of 58 mole percent by adding Zoo parts by weight of the alcohol to 24 parts by weight 96% sulfuric acid heated to 145 to 160 °. After washing the product with Water and alkali and drying over anhydrous potassium carbonate left the Ether as residue after the liquid in a distillation column with a Soil had reached a temperature of 177 ° at a pressure of 7 mm.

Method 2 The ether of C13 alcohol was prepared by 40o parts by weight of the alcohol with 25 parts by weight of p-toluenesulfonic acid and 175 cm3 of heptane was heated to reflux conditions as a water entrainer. After the theoretical The amount of water had passed and the product was washed with water and aqueous alkali was, you got the ether from a boiling point of 151 to 155 ° below 7 mm in one 59 mole percent yield.

Method 3 The ether of the C18 alcohol was obtained by heating it for 21/2 hours with 10 parts by weight of 96% sulfuric acid to 145 ° to 150 °. After the reaction mass with water and a solution of 1 0/0 Na 0 H washed in 17.5 e / Eiger sodium chloride solution and was dried over potassium carbonate, the product was less than 7 mm above to 2o7 ° at 186th The yield was 56 mole percent.

High pressure lubricants can be made by taking the ether small amounts of, for example, 2 to 3o percent by weight of an extreme pressure additive adds, which contains sulfur, phosphorus and / or halogen, such as the known hydrocarbon derivatives, which contain both active halogen and active sulfur. Ether how they look the C18 to C18 oxo alcohols are particularly suitable for this purpose.

If, for example, the ether 3 ° / o Tricresyl phosphate added, the lubricant keeps the entire load of the Almenmaschine off.

These ethers can also be used with V.L improvers, antifoam agents, Pour point depressants and antioxidants are mixed. You can go with other lubricants such as mineral oils, esters, formals, mercaptals, polyethers and oxidized mineral oils, are mixed and used as additives for lubricants will.

Lubricating greases according to the invention can be prepared by adding a suitable metal soap, advantageously an alkali or alkaline earth soap of a high molecular weight fatty acid of 10 to 30 carbon atoms or a soap-salt complex from the soaps of high molecular weight fatty acids and the salts of low molecular weight fatty acids, to the ether, such as acetic acid, furancarboxylic acid, acrylic or similar acids in fat-forming amounts of, for example, about 5 to 40 percent by weight. The metal soap or the soap-salt complex can be added as such. For example, the pre-formed dry soap or the complex can be slurried into the carbonate and the mixture heated to 149 to 260 ° with stirring until a homogeneous mass is formed, which results in the finished fat on cooling.

The production of fats according to the invention is illustrated by the following examples. Example i A high molecular weight branched chain ether was prepared by treating a C13 oxo alcohol at 150 ° with sulfuric acid. After complete dehydration, the crude ether was washed, dried and distilled. The properties of the purified product were as follows: C13 oxoethers Straw-colored appearance liquid Flash point, ° C. . . . . . . . . . . . . 193 Viscosity, cSt at 98.9 ° .............. 3.29 at 37.8 ° .............. 14.63 at -40.0 °. ... .. ... .... . 6448, o Pour point, ° C. . . . . . . . . . . . . . C - 54 In the production of the lubricating greases, both pre-formed dry lithium soaps of high molecular acids (Li hydrofolates 54 *)) and complex soaps were used, for which equal molar proportions of hydrofolic acids 54 and acetic or crotonic acid were neutralized together with Li OH and dried. Composition by weight percent Complex Li soap from jointly neutralized hydrofol- acids 54 and acetic acid (molar - ratio i: i) ..................... 10 C13 Oxoether ...................... 79 Phenyl-alpha-naphthylamine as oxy- dation inhibitor ...: ............. i The dry soap was slurried with the ether and then heated together with this to 20 ° until complete dissolution had occurred. Then inhibitor was added. The fat can be cooled by pouring it into pans or by stirring it in a water-jacketed kettle. The finished fat is a smooth, even, short-fiber product.

*) Hydrofolic acids 54 are hydrogenated fish oleic acids whose unsaturated content corresponds approximately to 5-tearic acid. properties Drop point, ° C ........... 199 Penetration at 25 °, min / io unprocessed ............ 220 (after weak Homogenization of the cake) processed with 6o double over ................ 240 processed with ioo ooo Double strokes .......... 265 Lubrication in BEC- Excellent Machine (temperature lubrication without change at 3500 rpm; Tendency to be fibrous Standard BEC warehouse) and off to be removed from the warehouse flow, at 27 °, 66 °, 98.9 °, 135 ° Oxidation resistance according to Norma-Hoffmann (Bomb; waste of the sour fabric pressure around 0.35 kg / cmz), Hours ................ 235 Water solubility. . . . . . . . . . In boiling water insoluble Example 2 The ether and the complex soap were prepared and mixed according to Example i. Composition by weight percent Complex Li soap from jointly neutralized hydrofol acid 54 and crotonic acid (molar ratio i: i) ..................... 5 C13 oxoether ...................... 94 Phenothiazine as an inhibitor ......... T properties Drop point, ° C .............. 171 Penetration at 25 °, mm / 10 unprocessed ............... 295 processed. with 6o Double strokes ............ 310 edited with ioo'ooo Double strokes ............ semi-liquid, but keeps Fat structure Example 3 Attempts to disperse either simple lithium soap or complex soaps in oxophosphates resulted in almost complete dissolution of the soap in the phosphate and little or no fat structure was obtained. By using the Cla oxoether as a lubricant base and dispersing agent for the soap and the subsequent addition of C3 oxophosphate, an excellent fat product can be obtained. Production The dry complex soap was slurried in the C13 oxoether and the mass was heated to 2o4 ° or until the soap was completely dissolved in the ether. Then inhibitor was added and the mass was cooled to 149 ° to T21 ° with stirring, the C3 oxophosphate was added and stirred into the fat. The C8 oxophosphate was a commercial product. It can be made from C $ oxo alcohol and P 0 C13 (phosphorus oxychloride). The finished fat had good stability and showed no oil excretion.

Because of the stability of the C13 and higher oxoethers, fats can be produced by making the soap in situ in the ether, d. i.e., you can use fats or Saponify acids and with strong alkaline solutions in the presence of the ether neutralize.

Claims (7)

PATENT CLAIMS: i. Use of ethers of the general composition RO-R ', in which R and or or R' are branched-chain hydrocarbon radicals with at least 8, expediently = 0 to 20 C atoms, expediently with a pour point below about -7 ° and a flash point above 149 ° alone or in a mixture with other substances suitable as lubricants as lubricants. 2. Use of ethers after Claim i as a lubricant, which also z. B. increasing the resilience of the ether Regulators, expediently contain tricresyl phosphate. 3. Use of ethers according to claim i in which at least one of the residues is derived from oxo alcohol. 4. Use of Ethers according to claim i, which dieters are C13 oxo alcohol. 5. Use of Ethers according to claim i as a lubricant, which also has a fat thickener in fat-forming Contains quantities. 6. Use of ethers according to claim 5 as a lubricant with a complex metal soap as a thickener, which contains the residues of a high-molecular-weight fatty acid and a low-molecular-weight fatty acid Contains carboxylic acid. 7. Use of ethers according to claim i as lubricants, which also contains the phosphate of an oxo alcohol in a smaller amount than the ether.