DE974140C - Process for improving the solubility and miscibility of naphthenic acid salts which contain monovalent or polyvalent cations in or with hydrocarbons - Google Patents

Description

Process for improving the solubility and miscibility of naphthenic acid Salts containing mono- or polyvalent cations in or with hydrocarbons Naphthenic acid salts, such as the barium and aluminum salts, can be mixed with organic solvents, especially hydrocarbons, as impregnation, Lubricants or pesticides and in the manufacture of plastics use. However, their usefulness is limited by the fact that they in particular form gels with hydrocarbons which have no fluidity and therefore difficult or impossible to mix with low or high molecular weight hydrocarbons) leave, so in aliphatic, cycloaliphatic or aromatic hydrocarbons are difficult to dissolve.

For many purposes it is desirable to have the more or less high viscosity of solutions of naphthenic acid salts with mono- or polyvalent cations in organic solvents, especially in hydrocarbons.

The process of the present invention uses polyalkylene glycol derivatives for this purpose certain composition.

US Pat. No. 2,448,664 discloses the action of i, 2-propylene oxide known to aliphatic monoalcohols. Some of the resulting monooxy-i, 2-polyoxypropylene monoethers are miscible with paraffin hydrocarbons.

U.S. Patent 2,520,612 describes the manufacture of dieters of the polyoxyalkylenes by the action of, for example, dimethyl sulfate on the polyoxyalkylenes.

It is also known (A. Russ in Seifen, Öle, Fette, Wachse, Vol. 77, 1951, p. 176) that the low molecular weight ethylene glycol ethers are used because of their pronounced dissolving power for natural and artificial resins, collodion wool, celluloid, cellulose ethers and also chlorinated rubber in industry. The action of ethylene oxide on naphthenic acids is also known from British patent specification 67o 153. In this way, products with an improved odor and improved emulsifier properties are obtained.

Rust inhibitors are described in TTSA Patent 2,564,422. These contain partially esterified polyhydric alcohols as an active substance, like glycerol monooleate, which are brought into solution by oil-soluble amine salts.

The German patent specification 261 070 describes the addition of naphthenates to mineral oils. However, this addition increases the viscosity of the mineral oils quite significantly.

U.S. Patent 2,554,222 describes improving water resistance of oily lubricants that are thickened by inorganic gels, such as silica gels or are gelled by adding hydrophobic cation-active substances such as N-cetylpiperidine. As an oily lubricant, thickened by silica gel and hydrophobic by means of Cation-active substances are made water-resistant, here are petroleum hydrocarbons called, in a particular embodiment of the process, also polyalkylene oxides or polyalkylene glycols. Thus, while in this U.S. Patent 2,554,222 these Compounds used as the main ingredient of lubricants are the Otherwise, polyalkylene glycol derivatives not claimed in this citation used according to the present invention only as a solubilizer for naphthenates.

U.S. Patent 2,559,521 relates to the manufacture of lubricants, which consist of esters of dicarboxylic acids, the carbon chain of the dicarboxylic acid is interrupted by 0 or S atoms. These lubricants have a high viscosity index, thus a low dependence of the viscosity on the temperature. These synthetic However, lubricants do not contain any additives that affect viscosity.

U.S. Patent 2,124,782 describes the manufacture of insecticides effective pesticides made from hydrocarbon oils, naphthenates and glyceryl or glycol monooleate, which are sprayed in the form of aqueous emulsions. It finds There is a note that specifically glyceryl oleate or glyceryl naphthenate the viscosity of naphthenate solutions. About those to be used according to the invention for this purpose Nothing is said about polyalkylene glycol derivatives; the superiority of these compounds compared to the compounds mentioned in the above-mentioned USA patent specification is further demonstrated below in experiment II.

Furthermore, in the British patent 491501 anti-rot agents described that from concentrated solutions of metal naphthenates in hydrocarbons and those for better emulsification in water »Emulphor o« (manufactured from 1 mol of oleyl alcohol and 20 mol of ethylene oxide) is added. "Emulphor o" proves proved to be unsuitable for the present purpose, as demonstrated in Experiment I below will be. According to the prior art mentioned, the following is therefore known: a) The addition from naphthenates to mineral oil, b) the use of oil-soluble polyalkylene glycol derivatives instead of oily hydrocarbon-based lubricants (not together with Hydrocarbons), c) good dissolving power of the low molecular weight glycol derivatives for some resins, d) the addition of hydrophobic, cationic substances to oil Sniffing agents thickened with inorganic gels, e) the use of certain dicarboxylic acid esters as valuable lubricants, but which do not contain any additives contain, f) the mixture of hydrocarbon oils, naphthenates and glyceryl or glycol monooleate and g) a concentrated solution of metal naphthenate in mineral oil, which also contains "Emulphor o".

A generally applicable procedure has now been found to achieve a good one Solubility and miscibility of naphthenic acid salts in or with hydrocarbons by reducing the viscosity of these solutions Substances polyalkylene glycol derivatives of the formula XO- (R-O) ", -R-OY added at go up to = 50 °, in which R is an alkylene radical with 2 or 3 carbon atoms, n is an integer of 2 to 7, which indicates the average degree of polymerization, X is an alkyl, aralkyl, Alkaryl, aryl, cycloalkyl, especially naphthene, or also an acyl radical with more than 6, in particular more than 8 carbon atoms and Y hydrogen, one Alkyl, aralkyl, alkaryl, aryl, cycloalkyl, especially naphthene radical or a Mean acyl radical.

The alkyl radicals are hexyl, 2-ethylhexyl, n-octyl, dodecyl, tetradecyl, Oktadecyl, Oktadecenylreste and the residues of such alkanols to be understood by Reduction of natural or synthetic fatty acids by hydrogenation of carbohydrates normal or increased pressure, obtained by oxo synthesis or by paraffin oxidation became.

Aromatic residues are: phenyl, dibutylphenyl, dodecylphenyl, naphthyl, Heptylnaphthyl, hexadecylnaphthyl, benzyl, phenylethyl and phenyloctadecyl.

Alicyclic radicals are: methylcyclohexyl, butylcyclohexyl and completely hydrogenated derivatives of mono- or polyalkyl- or aralkyl-substituted phenols or naphthols.

The acyl groups listed below can be used as acid residues Carboxylic acids used are caproic acid, capric acid, lauric acid, myristic acid, Oleic acid, rapeseed oil fatty acid, castor oil fatty acid, oxystearic acid, paraffin oxidation fatty acids, also benzoic acid, benzylbenzoic acid, alkylbenzoic acid, phthalic acid, naphthenic acid, Phenyl stearic acid and oxyphenyl stearic acid.

To carry out the present method, for example the following compounds are used: dodecylpentaethylene glycol, octadecenylhexaäthy-Ienglykol, 2-ethylhexylpentaethylene glycol, nonylheptaethylene glycol, phenylethylpentaethylene glycol, Methylcyclohexyloctaethylene glycol, p-octylphenyltetrapropylene glycol, dodecylcyclohexylhexapropylene glycol, hexylnaphthyltetraethylene or propylene glycol.

As polyalkylene glycols etherified on both ends, for example Dodecyl or lauryl pentaethylene glycol methyl ether, p-methylcyclohexyl tetraethylene glycol octyl ether, p-Octylphenyltetraethylene glycol isopropyl ether, octadecenylhexaethylene glycol phenylethyl ether and- 2-Äthylhexylheptaäthylenglykolbenzyläther use.

Of the polyalkylene glycols esterified on one or two sides, suitable particularly: pentaethylene glycol monostearate, hexaethylene glycol monostearate, dodecylbenzylpentapropylene glycol oleate, Octadecyl diol pentaglycol isopropyl ether, benzoyl pentaethylene glycol oleate, benzoyl heptaethylene or propylene glycol octyl ether, benzoyl pentaethylene or propylene glycol butyl ether.

According to the invention, instead of the polyalkylene glycol derivatives mentioned mixtures thereof can also be used.

The preparation of solutions of naphthenic acid salts in solvents, especially in hydrocarbons, can take place in a manner known per se, wherein it is immaterial in which form or order the mixture of naphthenates is used and polyalkylene glycol derivatives. You can z. B. the starting materials mentioned mix with each other, preferably with stirring in the heat, or to form a solution, a gel or a suspension of a naphthenate in a hydrocarbon Add polyalkylene glycol derivative. A solution of a polyalkylene glycol derivative can also be used add the naphthenic acid salt to hydrocarbons while stirring. Finally you can Both substances are also dissolved in each case in the desired hydrocarbons and the solutions are mixed together.

The solution to the naphthenate. Required amount of polyalkylene glycol derivatives can vary within wide limits, for example from one percent by weight, based on the amount of the used I. Zoo parts of light petroleum (b.p. 760 = 18o viscosity at 2o ° up to 24o °) .......................... 8o parts of Ba-Dinaphthenate ................... 798 ° Centistokes Zoo parts I. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Viscosity at?, O ° 1 part ocenol pentaethylene glycol ether ....... 159.4 centistokes II. Zoo parts benzene. . . . . . . . . . . . . . . . . . . . . . . . . . . Viscosity at 2o ° Zoo Parts Ba-Dinaphthenate ................... 371.1 Centistokes Zoo Part II ................................ Viscosity at 2o ° 1 part ocenol pentaethylene glycol ether ....... J 7o, 6 centistokes III. Zoo parts cyclohexane. . . . . . . . . . . . . . . . . . . . . . . . Viscosity at 2o ° Zoo parts Ba-dinaphthenate ................... non-flowing gel Zoo. Part III. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Viscosity at 2o ° i part ocenol pentaethylene glycol ether ....... 1941.6 centistokes IV. Zoo parts spindle oil (D.2 ° = o, 827, viscosity 4.6 Engler at 20 °, flash point 158 °) Viscosity at @ o ° 7o parts of Ba-Dinaphthenate. . . . . . . . . . . . . . . . . . , 755 centistokes Zoo parts IV ..... .... ...... . ..... ..... .... viscosity at 2o ° i part ocenol pentaethylene glycol ether ....... #: z84.7 centistokes Naphthenate, up to equal parts by weight or more. The amounts to be added depend both on the type of naphthenate used and on the solvent used and on the desired viscosity of the solution. These quantities can easily be determined through appropriate preliminary tests. It is expedient to work at an elevated temperature, e.g. B. at 9o to 15o °, but the process can also be carried out depending on the solution properties of the naphthenate at a higher or lower temperature.

The invention is illustrated by the following examples will. Example i a) Neutral barium naphthenate from distilled naphthenic acids the acid number 18o is a brittle resin at normal temperature, which at about 100 ° turns into a rubbery state and has a dropping point of over 230 °. It is very difficult to dissolve in mineral oils and forms viscous after cooling Jelly. One obtained by high pressure hydrogenation from a paraffin oxidation fatty acid Fatty alcohol with an average chain length of 16 carbon atoms and with a hydroxyl number of 6.8 was using 10/0 Na OH as a catalyst reacted with 5 moles of ethylene oxide and gave a waxy at room temperature Dimensions. with a dropping point of 38 °.

This oxyethylation product forms when mixed with mineral oils in some cases a slight sedimentation. If you now have 4o parts of barium naphthenate with 15 parts of said polyethyleneglycol ether with good stirring at about If 100 ° mixes, the rubber-like texture disappears, and one obtains after cooling a stringy syrup that is in hydrocarbons with no residue is easily soluble.

b) In solvents such as mineral oils, petroleum, benzene or cyclohexane, Bariumnaphtl nat forms a gel, which by adding alkyl polyethylene glycol ethers is liquefied. c) In tetrahydronaphthalene forms barium naphthenate Although not a gel, the viscosity of the solution is increased by adding the above Substances significantly reduced, as the following values show: 100 parts by weight Tetrahydronaphthalene and 20 parts by weight of barium naphthenate give a Solution with a viscosity averaging 15.5 centistokes. If you add ioo Parts by weight of this solution io parts by weight of lauryl pentaethylene glycol ether, see above the viscosity drops to 1.76 centistokes at 80 °.

EXAMPLE 2 The viscosity of a mineral oil of 18.7o centistokes at 80 ° increases after the dissolution therein of 10% by weight of potassium naphthenate to the value of 29.5 centistokes at 80 °. The addition of 20% decylpentaethylene glycol ether causes the viscosity to drop to 21.26 centistokes at 80 °.

The methyl ethers of des act in a similar way Parts by weight viscosity at ° C Naphthenate parts by weight of lauryl pentaethylene centistokes glycol oilers Al umini umnaphthenat ........... 1 - 80 ° 27.59 Aluminum naphthenate ........... 1 0.4 8o ° ig, 8o Aluminum and calcium naphthenate 5 - 8o ° 49.99 each Aluminum and calcium naphthenate 5 4 80 ° 30.00 each Zinc naphthenate ................. 30 - 80 ° 72.76 Zinc naphthenate ................. 30 4 8o ° 37.04 Iron naphthenate. . . . . . . . . . . . ... . 30-50,119.02 Iron naphthenate. . . . . . . . . . . . . . . . 30 4 50 ° io 8.2o Lead naphthenate ................. 30 - 50 ° 85.20 Lead naphthenate ................. 3o 4 50 ° 78, oo Example 4 The viscosity-lowering effect of one and the same naphthenate depends on the type of polyalkylene glycol derivative used, as can be seen from the values compiled in the table below.

To gels of aluminum naphthenate. in a liquid paraffinic Coal water fraction rides the boiling limit igo to 3–0 °, which is achieved by stirring of 10 parts by weight of aluminum maphthenate with 10 parts by weight of the above Hydrocarbon fraction at = oo to iio ° had been produced, each became 4 Parts by weight of the in .'der. Table -.cited polyalkylene glycol derivatives- given and the viscosity of the solutions obtained is determined in a known manner. mentioned Polyethylene glycol ether or its benzoic acid ester.

Example 3 This example shows in which way the viscosity-lowering influence of lauryl pentaethylene glycol ether in various naphthenic acid salts.

The parts by weight of naphthenic acid salts given in the table below were each in 100 parts by weight of a paraffinic mineral oil (specific weight at 20 ° = 0.882, viscosity index = 89, Conradsen coking number o, ii, no petrol-insoluble components) at a temperature of 100 to iio ° stirred in until a homogeneous mixture was obtained, the viscosity of which was determined at 80 or 50 °.

The same solutions were then treated with the amounts by weight of lauryl pentaethylene glycol ether indicated in the table and the viscosity of these solutions was also measured at 80 or 50 °. viscosity Addition at 8o ° in Centistokes without addition ..........._. . ..... over 3000 Lauryl pentaethylene glycol ether ..... 155 to 17o Benzylpentaethylene glycol methyl - ether ....................... "... 184 Ethylhexylphenyloctaethylene glycol ether. . . . . . ,. . . . . . . . . . . . . . . . . . 428 to 458 Stearoylheptethylene glycol benzoic acid ester. . . . . . . . . . . . . . . . - _. i8oo to igoo Example 5 A solution of 30 parts by weight of calcium naphthenate in 100 parts by weight of a diesel oil hydrocarbon with a boiling point of 15.0 to 32o ° has a viscosity of 3.02 centistokes at 80 °.

If 8 parts by weight of methylheptaethylene glycol naphthenic acid ester are added to 100 parts by weight of this solution too, the viscosity at 80 ° drops to 2.74 centistokes.

Dissolve 10 parts by weight of potassium naphthenate in 100 parts by weight of one paraffinic hydrocarbon with boiling limits igo to 320 °, one obtains a solution with a viscosity of 1.33 centistokes at 80 °.

If 100 parts by weight of this solution are 4 parts by weight of heptaethylene glycol stearic acid ester added, the viscosity of this solution is increased to 1.16 centistokes at 80 ° and with an addition of 4 parts of pentaethylene glycol benzyl ether to i, og centistokes decreased at 8o °.

Example 6 A warm mixture of 30 parts of barium dinaphthenate and 70 parts of white spirit (aromatic content 18 °, / o, KP- = 14o to i85 °) gave the Cool a solid gel.

By adding 40 parts of one . The reaction product of 1 mole of dodecyl alcohol and 2 moles of propylene oxide resulted in a thin liquid solution with a viscosity of -3.15 centistokes at 50 °.

The advantageous results that can be achieved by the present method, also over those in U.S. Patent 2,124,782 and British Patent 4915o1 additives for naphthenate solutions described go from the following comparative experiments from: Experiment I: 10 parts of barium dinaphthenate are converted into 10 parts of a barium dinaphthenate at 120 ° C Dissolved mineral oil (flash point 232 ° C, pour point -21 ° C, viscosity at 50 ° C 62.1 cSt).

When it cools down, it creates a smooth, uniform gel. 100 parts each this gel is mixed with a) 0.5 parts of "Emulphor o" (British patent specification 491501).

"Emulphor o" does not dissolve in the gel at 20 ° C, but causes it a strong cloudiness of the mixture.

b) 0.5 part of octadecenyl octaglycol ether.

At 20 ° C., an optically clear solution and its viscosity were formed at 50 ° was 104.8 cSt.

c) 1.5 parts of octadecenyl octaglycol ether.

The resulting solution showed only a very slight turbidity at ao ° C. The viscosity of the mixture was at 50 ° 8o.6 cSt. Experiment II: To 100 parts of the gel specified in Experiment I were added: a) i, o parts of ethylene glycol monooleate. . (UNITED STATES.- b) 3.0 parts of ethylene glycol monooleate. c) i, o parts of triethylene glycol monooleate font d) 3.0 parts of triethylene glycol monooleate 2: 124 782). The viscosities were determined at 50 ° C. The following values were obtained: a) 563.1 cSt, b) io8, o cSt, c) 140.6 cSt, d) 78.2 cSt.

Claims (3)

PATENT CLAIMS: i. Process to improve solubility and Miscibility of naphthenic acid salts containing mono- or polyvalent cations, in or with hydrocarbons and to reduce the viscosity of the obtained Solutions by adding polyalkylene glycol derivatives as solubilizers, thereby characterized that these salts or their solutions are polyalkylene glycol derivatives the more general. Formula XO- (R-0) n-R-OY, in which R is an alkylene radical with two or three carbon atoms, n an integer from 2 to 7, X an alkyl, aralkyl, Alkaryl, aryl, cycloalkyl, especially a naphthene radical or an acyl radical more than 6, especially with more than 8 carbon atoms and Y i hydrogen atom, an alkyl, aralkyl, alkaryl, aryl, cycloalkyl, especially a naphthene radical or an acyl radical, or mixtures thereof with ordinary or elevated Temperature, preferably at up to 150 °, is added. 2. The method according to claim i, characterized in that naphthenates are those of metals of the i. to 4th group of the periodic system, especially of potassium, calcium, barium, magnesium, zinc, Aluminum and lead, can be used. 3. The method according to claim i and 2, characterized characterized that the naphthenates or their solutions are polyalkylene glycol derivatives added in an amount of 1 to 100 percent by weight and more. Considered Publications: Seifen - Fette - Öle - Wachse, Vol. 77, 1951, p. 176; U.S. Patents No. 2,448,664, 2,520 612, 2,564,422, 2,559,521, 2,554,222, 2,124,782; British patents No. 67o 153, 491501; German patent specification No. 261 o7o.