DE1013026B - Additive mixture to hydrocarbon oils, especially lubricating and motor oils - Google Patents

Description

It is known to add sulfonic acid salts to motor oils, about the decomposition products, such as resins, asphalt, tars, which arise while the engine is running and the like to keep in suspension. At the same time, this property frees the piston ring grooves held by resinous and coking products, so that a free play of the piston rings and oil scraper rings remains guaranteed.

It is also known to add calcium sulfonate to a lubricating oil in addition to another soluble organometallic compound. The latter is a barium salt of phenol sulfide derivatives. This mixture is used in turn with the simultaneous addition of high polymers of alkyl maleate vinyl acetate. The overall mixture should trigger various effects in the lubricating oil, namely on the one hand act as a detergent and on the other hand increase the viscosity. However, the components of the mixture are "incompatible" with one another, and therefore, among other things, polyalkylene glycol ethers should also be added, in which case at most a compound whose terminal group has 8 carbon atoms is considered. In connection with the addition of calcium sulfonate, a monoethyl ether is mentioned.

Finally, it is also known to use lubricating oils as high-pressure lubricating oils that are oxygen-rich, Adding highly polymeric substances that are sparingly soluble in the oil and acting as a solubilizer for the To add, inter alia, oil-soluble sulfonates and / or monoethers of polyalkylene glycols to high polymers.

It has now been found that the effect of the sulfonates is supplemented and increased when the motor oils Polyalkylene glycol derivatives are added and at the same time higher molecular weight ethers without a polyalkylene glycol group. The former group of substances, which has a plurality of ether bonds, is characterized by the formula

XO- (RO) _n -R-OY.

Here, R denotes an alkylene radical having 2 or 3 carbon atoms, η denotes an integer, namely 1 to 20 or more, in particular 2 to 7; X is a hydrocarbon radical with more than 8 carbon atoms, Y is a hydrogen atom or a hydrocarbon radical with any number of carbon atoms.

As higher ethers without a polyalkylene glycol group, those are to be used in which at least one radical has 6 or more carbon atoms.

The sulfonates to be used according to the present invention are salts, surface additive mixture to hydrocarbon oils, especially lubricating and motor oils

Applicant:

Rhein-Chemie GmbH,
Mannheim-Rheinau

Dr. Rudolf Kern, Neustadt an der Weinstrasse,

and Dr. Hans Scheurer, Heidelberg-Schlierbach,

have been named as inventors

active sulfonic acids, preferably alkaline earth sulfonates, or salts of heavy metals such as lead, zinc, tin,

Magnesium et al. Into consideration. Oil-soluble amine salts or ammonium salts can also be used, e.g. B. sulfonic acid salts of triethanolamine, tributylamine, dicyclohexylamine and others
Suitable sulfonic acids are: Petroleum sulfonic acids, such as are obtained in oil-soluble (mahogany sulfonic acid) or oil-insoluble ("green sulfonic acid") form in the sulfuric acid refining of mineral oils, and straight-chain or cyclic sulfonic acids, which in turn can be substituted.

The following are mentioned as individual compounds for illustration: fatty alkylsulfuric acid esters, n-alkylsulfonic acids, Fatty alkylbenzenesulfonic acids, dialkylnaphthalene sulfonic acids, naphthenylbenzenesulfonic acid.

Examples of suitable polyalkylene glycol derivatives are: dodecylpentaethylene glycol, Octadecenylhexaethylene glycol, nonylheptaethylene glycol, phenylethylpentaethylene glycol, methylcyciohexyloctaethylene glycol, p-octylphenyltetrapropylene glycol, dodecylcyclohexyl hexapropylene glycol.

Ethers of dodecyl alcohol, e.g. B. dodecyloctyl ether, especially dodecyl-2-ethylhexyl ether. Other ethers without a polyalkylene glycol group, which should preferably be used in the present case, are, for example, the following: Di-n-hexyl ether, di-noctyl ether, di-η-nonyl ether, di-2-ethylhexyl ether, lauryl-2-ethylhexyl ether, octadecene-9- yl-l-isobutyl ether, dodecylphenyl ether, lauryl cyclohexyl ether, octyl - ß - tetralol ether, nonyl - 4 - methyl - cyclohexyl ether, 4-octylphenyl-2-ethylhexyl ether; also the benzyl ethers or alkyl-substituted benzyl ethers of the mentioned or other aliphatic or alicyclic alcohols, for example nonyl benzyl ether, octadecenyl-4-methylbenzyl ether, dibenzyl ether, tetra

709 590/320

hydronaphthylmethyl-co-phenyl or -benzyl ether, also tetrahydronaphthylmethyl - ω - 2 - ethylhexyl ether, butanediol (1,3) monooctyl ether, butanediol (1,4) dibenzyl ether, butanediol (1,4) isobutyldodecyl.

Also the ethers of paraffin fatty alcohols or their precursor alcohols and of oxo or naphthene alcohols are advantageously used, for. B. paraffin fatty alkyl cyclohexyl ether, dodecyl - first run fatty alkyl ether, whereby under initial alcohols a mixture of such alcohols is to be understood, as they are by High pressure hydrogenation of paraffin fatty acids and subsequent distillation of the alcohols formed incurred as first runnings, the resulting mixture having a chain length of 6 to 9 carbon atoms. Naphthenic acids, such as those obtained during the refining of mineral oils, can be reduced by high pressure or according to Bouveault-Blanc the produce corresponding naphthenic alcohols, which can be easily converted into their ethers and which in turn can be used advantageously by the process according to the invention. As examples of this may be mentioned: the dinaphthenyl ether and the naphthenylbenzyl and -2-ethylhexyl ether.

The use has proven to be very advantageous such high-boiling mono- or diether proved that at room temperature, for example at 20 ° C, are liquid.

The combined use of polyalkylene glycol derivatives and higher-boiling ethers without Polyalkylene glycol groups according to the present invention offer several advantages. So is It is noteworthy that both groups of substances increase the viscosity of engine oils, which have a certain content have sulfonates, and it has been shown that they are lower in terms of the pour point and viscosity enhancement supplement. This is shown in the following table, in the pour point and viscosity of an engine oil containing a sulfonate are given under 1. and under 2. to 4. the same properties after adding various additives to be compared here. As a base oil A paraffin-based mineral oil with the following characteristics was used:

Pour point in ° C -19

Viscosity at 50 ° C in cSt 62.1

Pour point
in ⁰ C viscosity
at 50 ° C
in cSt 1. 100 parts base oil drip +5 parts barium octa- Point decylbenzenesulfonate + 38 ° solid gel 2. like 1. +1 part octadecenyl pentaethylene glycol ether - 21st 82.3 3. like 2. -f-l part dodecylethyl hexyl ether -19 32.6 4. like 1. + 1 part dodecylethyl schmie hexyl ether -20 gel

A firm gel is formed by adding 5 parts of barium octadecylbenzenesulfonate to the base oil (Example 1), which by adding 1 part of octadecenylpentaethylene glycol ether (Example 2) in a solution passes over which has a slightly lower pour point than the base oil, but one at 50 ° C has 20 cSt higher viscosity. Now this solution of base oil + sulfonate + polyalkylene glycol ether 1 part of dodecylethylhexyl ether is added (Example 3), the viscosity is reduced by 50 cSt. If, on the other hand, the dodecylethylhexyl ether is a base oil sulfonate mixture without a polyalkylene glycol ether added (Example 4), there is practically no change in viscosity, but it is the pour point recognize degrading influence. This solid gel as in Example 1 can therefore be diluted cannot be converted into a liquid lubricating oil with the dodecylethylhexyl ether, but it does succeed this if a polyalkylene glycol ether is added.

The ethers used according to the invention also complement each other particularly with regard to their dissolving and Dispersing effect on the resinous or asphalt-like or other decomposition products of the Motor oil.

For the polyalkylene glycol derivatives to be used according to the invention and higher-boiling ethers can be used instead of just one component. The ones to be added Quantities can vary within very wide limits and, for example, in the case of polyalkylene glycol derivatives between 1 and 100 percent by weight, based on the amount of sulfonate used, or more, while with the higher-boiling ethers they can be up to 200 percent by weight and more; she are not only dependent on the type and amount of sulfonic acid salts or mixtures thereof as well as their own chemical nature, but also from the desired improvement in solubility or miscibility of the sulfonic acid salts in the hydrocarbon oils and the desired viscosity of these solutions.

Solutions of sulfonic acid salts in hydrocarbons in the presence of high-boiling ethers and polyalkylene glycol derivatives can be prepared in various ways. How this is done depends on the sulfonates, polyalkylene glycol derivatives, ethers and the oil into which these substances are to be mixed, from the particular sulfonates used. To work as at 50 to 250 ^Q C, preferably between 100 and 200 ° C. So you can z. B. dissolve sulfonates in the ethers, add polyalkylene glycol derivatives to these solutions and dilute the solutions with hydrocarbon oils. It is also possible first to prepare melts, pastes or the like of sulfonic acid salts with polyalkylene glycol derivatives, add ether to these mixtures and these total

add mixture to hydrocarbons. Furthermore, you can first prepare a solution of hydrocarbons, ethers and polyalkylene glycol derivatives and dissolve the sulfonic acid salts in this.
Finally, sulfonic acid salts and polyalkylene glycol derivatives can each be dissolved separately in ethers and both solutions can be combined. This mixture dissolves easily in hydrocarbon oils.

In many cases it has proven to be expedient to add sulfonates and naphthenic acid salts to the motor oils at the same time using the two substances to be used according to the invention as solubilizers. The implementation is then again preferably in the form that first a mixture of ¹ vbnl sulfonates and naphthenic acid salts with the two "

Manufactures substances and uses this mixture as an additive for alloying motor oils.

The new engine oil additives also develop in cold engines, i. H. at low oil temperatures for example 40 to 50 ° C, good effectiveness.

The amounts of additives to be added to motor oils depend on a number of factors away. These are:

The quality of the engine oils or other lubricating oils, the intended running time and load of the engine without changing the oil, the sulfur content of the fuels, etc.

The worse the quality of the engine oils, lubricating oils or the like, the longer the running time of the engines and the higher the sulfur content of the fuels, the higher the content of additives to be chosen.

In general, the amounts of the additives vary between 1 and 25 percent by weight, based on weight on engine oil, lubricating oil or the like. However, lower or higher additives can also be used come.

A good homogeneous distribution of the additive - mixture of sulfonic acids and naphthenic acids Salts, polyalkylene glycol derivatives and higher-boiling ethers · - in motor oils or lubricating oils is in turn achieved if you mix these mixtures at temperatures of about 40 to 60 ° C or higher. For example, temperatures of up to 150 ° C can also be used. In many cases, however, a homogeneous mixture is achieved even at lower temperatures.

In addition to the additives mentioned, known pour point or viscosity improvers can also be added to the lubricating oils as well as anti-aging agents or antioxidants are added, z. B. alkyl-substituted Phenols or cresols, compounds containing divalent sulfur, and also secondary ones aromatic amines, phenothiazines, phosphoric or thiophosphoric acid esters, salts of thiophenols.

example 1

In 20 parts of coconut lauryl pentaethylene glycol ether and 27 parts of lauryl ethylhexyl ether, 35 parts were added Barium mononaphthenate and 15 parts of barium alkylbenzene sulfonate, the alkyl radical corresponding to a chain with 14 carbon atoms, with stirring and heating Dissolved up to 150 ° C. Then 3 parts of di-tert-butyl-p-cresol were added admitted.

5 parts of this mixture were added to 95 parts of a base oil, which was prepared by suitable mixing was produced by brightstock machine and spindle oil and had the following key figures:

Density at 20 ° C 0.905

Pour point -37 ° C

Viscosity at 50 ° C 44.9 cSt

PY 73

Coke content according to Conradson 0.29%

This oil mixture was tested in practice in a Mercedes-Benz 170 V passenger car. Before starting this test, the pistons had been removed and completely cleaned. The test run extended over 5500 km, with oil being changed after 500, 1500 and 3500 km.

At the end of this test run, the pistons showed a completely metallic appearance, all of them Rings were free to move, and only in the

60 piston ring grooves showed slight sludge deposits.

Example 2

A product with the following composition was produced:

50 parts of the barium salt of a petroleum sulfonic acid. The underlying acid for this had a molecular weight of 450. 30 parts of dodecyl tetraethylene glycol ether, 17 parts of dodecyl ethylhexyl ether (Bp. 12 mm: 185 to 190 ° C), 3 parts of ethylhexylphenol.

5 parts of this mixture became 95 parts of a mixed base oil with the following characteristics added:

Density at 20 ° C 0.885

Flash point 236 ° C

Viscosity at 20 ° C 336.4 cSt

at 98.9 ⁰ C ll, 59 cSt

PY 98

Coke content according to Conradson 0.16%

SZ 0.18

VZ 1.65

Ash 0.02%

This alloyed oil was tested in a 1 - cylinder 4 - stroke diesel engine. Of the The engine had an output of 12 HP at a speed of 1500 rpm. The test run lasted 120 hours at full load and 100 ° oil temperature. An oil change was not made, but only the used oil gave way. A Middle Eastern diesel oil was used as fuel had a sulfur content of about 1%.

After the end of the test run, the flask had a clean, shiny appearance on the outside. All Piston rings were completely free to move. The oil control rings and the oil ring grooves were clean, blackening was found only in the uppermost ring grooves.

In comparison, the corresponding base oil was made without any further addition and on the same Test bench and driven under exactly the same conditions as specified above. This test run had to be canceled after 80 hours because of the ring stuck. After expansion It turned out that one piston ring was completely glued in place, the other heavily restrained. That The exterior of the piston was black. In all ring grooves and in the slots of the oil control rings a thick layer of mud and coke had built up. The inside of the piston was also thick black lacquer layer coated.

Claims (4)

Patent claims: 1. Additive mixture to hydrocarbon oils, especially lubricating and motor oils, consisting from sulfonic acids, salts and etherified polyalkylene glycols the general formula XO - (R - O) _n - R - OY, where R is an alkylene radical with 2 or 3 carbon atoms, η is an integer from 1 to 20, in particular 2 to 7, X is a hydrocarbon radical with more than 8 carbon atoms and Y is a hydrogen atom or a hydrocarbon radical with any number of carbon atoms, and also of ethers without poly alkylene glycol groups in which at least one radical has more than 6 carbon atoms. 2. Additive mixture according to claim 1, characterized in that it contains fatty alcohol polyalkylene glycol ethers in which X is a hydrocarbon radical with 12 carbon atoms. 3. Additive mixture according to claim 1 and 2, characterized in that the ethers without a polyalkylene glycol group Ether of dodecyl alcohol, preferably dodecyl octyl ether, in particular
Are dodecyl-2-ethylhexyl ether. I ¹ I 4. Zusatzmischuwg according to claim 1 to 3, ge | ¹ then identifies acid salts by an additional content of naphthenic Ί. Considered publications:
German patent application N 4864IV c / 23c;
British Patent No. 676,625.