DE1094905B - Additives for fuel and lubricating oils - Google Patents

Description

GERMAN

The invention relates to the use of novel, valuable surfactants of an ionic nature, the contain both an anionic and a cationic group in the same molecule, as additives for fuel and Lubricating oils.

According to the invention, the use of novel and technically valuable compounds of the formula

R ₁ -Ar-

R ₂ -Ar-CH _{2 R}

in which R ₁ and R _{2 are} alkyl groups with 9 to 18 carbon atoms, Ar is a mononuclear aryl group, R _{3 is} an alkyl group with 1 to 7 carbon atoms and R _{4 is} an alkylene group with 1 to 7 carbon atoms, proposed as dispersing and rust-preventing additives. By adding the compounds according to the invention, many of the disadvantages that have hitherto occurred in practice when using fuel and lubricating oils can be avoided.

Since these compounds are amphoteric in nature, they show the useful ones in a single compound Properties of both cationic and anionic surfactants are exceptional surface-active properties that are neither exclusively cationic nor anionic compounds Exhibit nature.

Another special feature of the compounds used according to the invention can be seen in the fact that the quaternary nitrogen group is more ionizable than an ordinary one under certain conditions Amino group under the same circumstances. So show z. B. the present compounds under alkaline conditions, as they are often encountered in the application of surface-active agents, the characteristics free zwitterions and can be ionized as such, whereas aminosulfonates under the same conditions do not have the character of zwitterions.

The compounds used according to the invention are preferably oil-soluble and can be excellent in Disperse lubricating and fuel oils. The sludge-forming substances present in fuel oils under normal conditions This means that substances can be kept in suspension for an indefinite period of time, which is undesirable Sludge deposits and filter blockages can be avoided. At the same time they are used as anti-rust additives very effective for fuel and lubricating oils.

The compounds according to the invention, illustrated by the structural formula above, contain two alkaryl radicals, each of which by a methylene residue with nitrogen connected is. Examples of suitable alkaryl groups

Applicant:

California Research Corporation,
San Francisco, Calif. (V. St. A.)

Representative: Di.-Ing. H. Ruschke, Berlin-Friedenau,

and Dipl.-Ing. K. Grentzenberg,
Munich 27, Pienzenauer Str. 2, patent attorneys

Richard D. Stayner, San Francisco, Calif. (V. St. Α.),
has been named as the inventor

are alkylated benzene, naphthalene, anthracene, toluene, Xylene, mesitylene groups, etc., of which alkylated benzene and toluene groups are preferred because they are readily available and impart high efficacy to the compounds in which they are contained. The nuclear alkyl substituents can be straight or branched chain and contain 9 to 18 carbon atoms. The alkyl groups can be derived from halogenated hydrocarbons, aliphatic alcohols, and olefins including cracked petroleum fractions and polymers of ethylene, propylene and butylene derive. Propylene polymers having 9 to 18 and preferably 12 to 15 carbon atoms are used for the present purposes per molecule preferred because of their chemical resistance, which is a characteristic of the moderate Chain branching of propylene polymers is in general.

In the above formula illustrative of the invention is the portion that differs from the N-alkylaminoalkanesulfonate derives, through the rest

> N - R ₄ -SCVT

reproduced. Suitable N-alkylaminoalkanesulfonates are sodium N-methylaminoethanesulfonate, also known as sodium N-methyltaurate, sodium N-ethylaminoethanesulfonate, Potassium - N - ethyl -2 - aminopropanesulfonate, sodium N-butylaminobutanesulfonate, sodium N-hexylaminocyclohexanesulfonate. Sodium N-methylaminoethane sulfonate or sodium N-methyl taurate are particularly preferred, as they are readily available and particularly well suited for the purposes of the invention.

009 678/471

The Ν, Ν-dialkylbenzyl-N-methyltaurine, which is the preferred one Embodiments of the invention are represented by the formula

/ χ ■ - - ■■■ - ■ - ■■■ ■

R ₁ - ¹ - j

χ J-CH ₂

- CH ₂ - CH ₂ - SO ₃ <->
CH,

reproduced, in which R ₁ and R _{2 are} alkyl radicals having 9 to 18 carbon atoms, R is hydrogen or methyl and χ is an integer between -1 and 3.

This preferred group of compounds according to the invention can e.g. B. by chlorine methylation nuclear Alkyl derivatives with 9 to Ϊ 8 carbon atoms of benzene, toluene or XyIoJ are produced. A molar excess of the chloromethyl derivative, preferably at least 2 mol, can then be mixed with sodium N-methyl taurate at a temperature between about 50 and 100 ° C in the presence of a neutralizing agent, e.g. B. of sodium hydroxide, sodium carbonate, sodium bicarbonate, etc., can be reacted.

The preparation of some of the compounds according to the invention is explained below. This manufacture is not protected within the scope of the present invention.

Production of
N, N-Di (nonylbenzyl) -N-methyltaurine

A mixture of 40 parts of sodium N-methyl taurate, 168 parts Nonylbenzylchlorid whose nonyl group derived from propylene trimer, 100 parts of ethyl alcohol and 75 parts of water was heated with stirring for 3 hours at 80 ⁰ C to reflux. The mixture was then diluted with 50 parts of methanol and extracted with 100 parts of petroleum ether. The aqueous layer was removed and the alcoholic solution was washed with 100 parts of water. Thereafter, 167 parts of a colorless solid substance were obtained by evaporation at 7O ⁰ C under reduced pressure.

Analysis for C ₃₆ H ₆₇ NO ₃ S

Calculated N = 2.45%;

. found N = 2.14%.

Production of
N, N-di (dodecylbenzyl) -N-methyltaurine

A mixture of 53 parts of sodium N-methyl taurate, 28 parts of sodium bicarbonate, 210 parts of dodecylbenzyl chloride, whose dodecyl group was derived from propylene tetramer, and 300 parts of ethyl alcohol became 8 hours heated to reflux at 80 ° C. The mixture was cooled and added with 100 parts of water and 20 parts of methanol diluted and the aqueous layer was removed. The alcoholic solution was made with 200 parts of petroleum ether and 150 parts of methanol and shaken. After separating the oily layer, there was evaporation the alcoholic solution obtained 161 parts of a light yellow, viscous liquid.

Analysis for C ₄₁ H ₆₉ NO ₃ S

Calculated N = 2.13%;

found N = 1.94%.

Production of
N, N-di (dodecylbenzyl) -N-methyltaurine

A mixture of 32 parts of sodium N-methyl taurate, 17 parts of sodium bicarbonate, 85 parts of water, 300 Share ethyl alcohol and 152 parts dodecylbenzyl chloride, whose dodecyl group from a light oil distillate with derived from about 12 carbon atoms per molecule, was refluxed for 6 hours. After removing the aqueous layer, the product was diluted with 100 parts of water and 100 parts of petroleum ether. The petroleum ether and the water layer was then removed. As the alcoholic layer evaporated, a viscous yellow smear obtained.

Production of 2- [N, N-di (dodecylmethylbenzyl) -N-ethylammonium] propane-1-sulfonate

CH ₃

CH ₂ \ = N-CH-CH ₂ • SO ₃
CH ₃ L C ₂ H ₆

A mixture of 189 parts of sodium 2- (N-ethylamino) propane-l-sulfonate, 800 parts of dodecylmethylbenzyl chloride, 84 parts of sodium bicarbonate, 378 parts of water and 500 parts of isopropanol were added with stirring Heated under reflux for 8 hours. After removing the aqueous layer, the product was washed with water. After drying, it was a pale yellow viscous liquid that made up 870 parts. In the above explanations, parts mean parts by weight, unless otherwise specified.

As starting materials for the production of fuel oils, their properties according to the invention by adding N, N - di - (alkylarylmethylene) - N - alkylammonium alkanesulfonates which can be improved are preferred Petroleum distillates boiling between 177 and 395 ° C, namely straight-run or cracked distillates, or mixtures those used whose specific gravity at 15 ° C. is at least 0.934, usually at least 0.904 amounts to. Without the additives of the present invention, these fuel oils form significant amounts of sludge and resin, which lead to clogging of the filters and the use of these oils in a continuously working Make operation impossible.

It has been found that very small amounts of the N, N - di - (alkylarylmethylene) - N - alkylammonium alkanesulfonates according to the invention of 1 percent by weight or less is absolutely effective in preventing clogging of filters and rusting - in the presence of Water in the system - inhibit. 0.001 to 0.20 percent by weight of N, N-dialkylbenzyl-N-methyltaurine with 9 to 18 carbon atoms in each of the alkyl groups suffice; 0.005 to 0.015 weight percent is preferred.

A rapid test method was used for the rapid evaluation of the fuel oils containing the additives according to the invention developed with the results found in practice on burners and diesel engines gives very good matching results. 500 ecm of fuel oil (with an additive of 0.01 percent by weight) mixed with 500 ecm of water, the 0.0102 percent by weight calcium plus magnesium carbonate (two thirds are calcium carbonate). The mixture is shaken in a separatory funnel for 30 seconds and then Let stand 10 minutes. An upper oil layer and a lower water layer with an opaque, more or less thick layer at the interface.

1

This interface layer is now through a fritted glass crucible sucked, and only as much oil and water are sucked through as for complete extraction of this layer are required, usually 25 ecm. In the case of strong emulsification, it may be necessary to use the. to filter the entire contents of the separating funnel. The resulting discoloration of the crucible due to the sludge and resin particles are used to determine the fuel oil quality with regard to the tendency towards filter clogging.

The filter is compared with eleven standard filters that are similarly used with fuel oils known filter clogging tendency and the numbers 0 to 10 - depending on the severity the deposit - wear. The interfacial deposition value so to be determined is on a fuel oil of the type specified above with the addition of various agents in Determined in comparison to a control sample:

Immersed in fuel oil with an additive of 0.005 percent by weight and moved in it. The results are as follows:

Table II

attempt

Table I.
Interfacial Deposition Value

attempt additive Found
value 1
2
3
4th N, N-Di- (C ₁₂ -polypropylene-
benzyl) -N-methyltaurine
N, N-Di- (C ₉ -polypropylenebenzyl) -
N-methyltaurine
Ν, Ν-Didodecylbenzyl-
N-methyltaurine
no addition 0
2
4th
10

Ν, Ν-di- (C ^ -polypropylenebenzyl) -N-methyltaurine .

N, N-di- (C ₉ -polypropylenebenzyl) -N-methyltaurine.

Ν, Ν-Didodecylbenzyl-N-methyltaurine

no addition

Anti-rust properties

in distilled
water
plus oil

no
rust

easier
rust

easier
rust

heavier
rust

Sea water plus oil

no rust

light rust

light rust

heavy rust

The fuel oils thus improved with the aid of the agents according to the invention can also contain further ones contain usual additives, so z. B. lecithin, oil-soluble alkylaryl polyglycol ethers, oil-soluble sulfonates, such as lead salts and petroleum sulfonic acids with 20 to 30 carbon atoms per molecule, oil-soluble naphthenates, alkali and lead salts of alkylphenol disulfides.

Claims (1)

Claim: Use of compounds of the formula This shows the superiority of the fuel oils provided with the agents of the invention. In experiments 1, 2 and 3 no or only very little filter deposits are recorded if the fuel oil contains one of the N, N-di- (alkylarylmethylene) -N-alkylammonium alkanesulfonates, while the fuel oil in experiment 4 contains an extraordinary one without any additive high deposition results. The fuel oils improved with the agents according to the invention were then tested with regard to their rust-inhibiting effect. The test was carried out according to ASTM method D-665-47 T. Steel spindles are turned into mixtures of distilled water and fuel oil with an addition of 0.001 percent by weight and of seawater and R ₁ -Ar-CH ₂ A +)
> -R ₄ -SO ₃ <-> R ₃ -Ar -CH _2R in which R ₁ and R _{2 are} alkyl radicals having 9 to 18 carbon atoms, Ar is a mononuclear aryl radical, R _{3 is} an alkyl radical having 1 to 7 carbon atoms and R _{4 is} an alkylene radical having 1 to 7 carbon atoms, as additives for fuel and lubricating oils. Considered publications:
German Patent Nos. 655 999, 710 680, 821208, 852 698, 876 383;
Schwartz-Perry: Surface active Agents (1949), 226. ι 009 678/471 12.60