DE1271454B - Motor fuel - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

ClOl

German class: 46a6-7

Number: 1271454

File number: P 12 71 454.4-44 Filing date: December 14, 1964 Opening day: June 27, 1968

Various nitrogen-containing derivatives of alkenyl succinic anhydrides high molecular weight are known as sludge dispersants for lubricating oils. This is particularly effective Reaction product of an alkenylsuccinic anhydride with a polyamine, such as tetraethylene pentamine. Such additives can be used in lubricating oils with regard to their sludge dispersibility further improve by the fact that the polyamine is first converted into a 2-imidazoline, which is then condensed with the alkenyl succinic anhydride. These additives reduce the deposition sludge in the crankcase and the formation of paint on the pistons. They are good too Corrosion retardants and improve the shelf life of the fuel. In the transport and storage, however, the fuel tends to come into contact with water sediments.

The additives described above now favor the formation of water dispersions in the fuel, and the entrained water easily causes carburetor freezing.

In addition, these dispersing additives favor the formation of gasoline-in-water emulsions, which are a waste of gasoline.

The invention has the object of providing a multi-purpose additive mixture (which the above-described Condensation products of imidazoline and alkenyl succinic anhydride as sludge dispersants contains) to create for motor fuels, which at the same time a practical causes complete separation of gasoline and water. Accordingly, the motor fuel is in accordance with of the invention with a content of an

H R ' HH

Motor fuel

Applicant:

Esso Research and Engineering Company, Elizabeth, N. J. (V. St. A.)

Representative:

Dr. K. Th. Hegel, patent attorney,

2000 Hamburg 50, Große Bergstr. 223

Named as inventor: Gerhard J. Pietsch, Elizabeth, N. J .; John D. Turner, North PlainfieM, N.J. (V. St. A.)

Claimed priority: V. St. v. America December 20, 1963 (332233)

Settlement product from a long-chain alkenyl succinic anhydride and an organic nitrogen compound as a sludge inhibitor characterized in that that he's a mixture

a) a condensation product of an alkenyl succinic anhydride and an imidazoline of the formula:

RC = CCC
H
HC

(CHA

N - (CHA-f NH (CHAt- N .N

C C '

II I

H O R "

in which R and R 'are hydrogen atoms or hydrocarbon radicals, but at least one of the two radicals is a hydrocarbon radical. and the total number of carbon atoms in the radicals R and R 'is 40 to 250, while R "is an aliphatic hydrochloride having 1 to 30 carbon atoms, a number from 2 to 3 and m a number from 0 to 10.

b) an alkylbenzenesulfonic acid, the alkyl group of which has 1 to 30 carbon atoms and

c) a reaction product of a polyalkylene glycol having 14 to 60 carbon atoms each

809 567,458

Carboxyl group-containing polymeric carboxylic acid and optionally a solvent oil contains.

The addition of esters of polyhydric alcohols on the one hand and salts of alkylbenzenesulfonic acids on the other hand to lubricating oils or fuels is known.

The alkenylsuccinic anhydrides can easily be converted into maleic anhydride with an organic compound that contains a double bond at one end. The reaction products correspond to the general formula, since these polymers are easily available and are inexpensive. A particularly preferred example of such an olefin polymer is polyisobutylene. In this case, R 'denotes a hydrogen atom and R denotes the remainder

CH,

CH ₃ -C-

CH,

CH,

CH ₃ -C

CH,

R '

R-CH = C-CH ₂ -CH C

CH, - C

',O

.0

20th

in which R and R 'can represent hydrogen atoms or unsubstituted or substituted (e.g. chlorinated or sulfurized) hydrocarbon radicals including aliphatic, alicyclic, aromatic radicals, etc., but at least one of these two radicals must be a hydrocarbon radical. The total number of carbon atoms in the radicals R and R 'is generally from 40 to 250, preferably from 70 to 120. The alkenyl part of the molecule is preferably derived from a molecular weight of about 700 to 3000, e.g. B. from about 800 to 1300, having polymer of a Co- to Cö-monoolefin, which with the maleic anhydride wherein n ' depends on the molecular weight of the polyisobutylene.

The production of alkenyl succinic anhydrides is z. B. from U.S. Patent 3018250, Example 1, column 3, lines 57 to 71, is known. In general, the maleic anhydride with the olefinic reactants simply heated in equimolecular amounts. As a diluent Inert solvents such as toluene, xylene, etc., can be used to reduce the viscosity of the reaction product if the alkenyl compound is very viscous, so that the reaction product can be filtered more easily. The solvent can be used later be evaporated. Under certain circumstances a high-boiling solvent can be used, which remains in the reaction product if it does not interfere with the end use purpose. This preparation of the alkenyl succinic anhydrides is illustrated by the following equation:

R '- CH ₂ -C = CH ₂ + C-

Il -c

ο ο RHH

H-C-H

Il -c

'? ο

in which R and R 'have the above meanings.

The imidazoline to be reacted with the alkenylsuccinic anhydride can by condensing a Carboxylic acid can be prepared with an aliphatic polyamine according to the following equation, in which a monocarboxylic acid is used:

R "COOH + H ₂ N (CH ₂ ) _n -ENH (CH ₂ ) _n fc -NH (CH ₂ )" NH ₂

> H ₂ N (CH ₂ ) _n —f NH (CH ₂ ) "

(CH ₂ )

-N

N + 2H ₂ O

Here, R "denotes the saturated or unsaturated aliphatic hydrocarbon radical of a fatty acid having 1 to 30, preferably 1 to 18 carbon atoms, η has the value 2 or 3 and m denotes a number from 0 to 10, preferably from 0 to 3. Instead of the in The monocarboxylic acid given in the above equation can also be used with dicarboxylic acids, in which case both carboxyl groups can react with the terminal amino groups of two different polyamine molecules.

Examples of acids that can be used are acetic acid, fumaric acid, capric acid, adipic acid, lauric acid, Oleic acid, linoleic acid, stearic acid, etc. Acetic acid is particularly preferred because it has an imidazoline the lowest possible number of carbon atoms. Because the acid isn't too much contributes to the end product, apart from allowing imidazoline formation, the end product appears to be a better sludge dispersibility per part by weight of the end product.

the lower the molecular weight of the acid. In other words: the higher acids carry apparently only adds to the bulk of the product without significantly improving it; therefore they diminish the effectiveness of the final product on a weight basis, but can still be used.

Examples of the polyamines which can be used in the above reaction are diethylene triamine, tetraethylene pentamine, Octaethylene nonamine, tetrapropylene pentamine, etc.

The imidazoline formation reaction between the acid and the polyamine can be accomplished by simply mixing stoichiometric amounts of the two reactants and then driving off the water of condensation be carried out by heating to reflux temperature. Optionally, an inert solvent such as heptane or Toluene, can be used as a water entrainer in order to promote the expulsion of the water of reaction. The solvent can then later be evaporated.

The third stage of the manufacturing process is the reaction of the imidazoline with the alkenyl succinic anhydride according to the equation

R ' H i υ + H ₂ N (CH ₂ ) "- fNH (CH ₂ )" 3 ^ r H O
Il / ² \ (CH ₂ ) Τ> ί ~ * ΊΊ Z " ¹ i Ζ ™ ¹ - ( Il ENH (CH ₂ ) "tN N + H ₂ O K LH - L. ι_
H / -ι ( * _ · R " H- V R ' H ( N (CH ₂ ) "H - ( K. ( ~ \ Il ) H H- H -1 -> R- -CH

R "

in which R, R ', R ", m and η have the above meanings. This third reaction stage is preferably carried out with equimolecular amounts of the two reactants with heating to the reflux temperature for the purpose of removing the water of condensation , an inert solvent can be used.

The additives described above promote the formation of water cloudiness in gasoline and the Formation of an emulsion in water consisting of the additive and the gasoline.

According to the invention, an additional combination is now used to completely separate gasoline and water used, which contains a benzenesulfonic acid and an ethoxylated dimeric acid.

Suitable benzenesulfonic acids are alkylbenzenesulfonic acids whose alkyl groups are 1 to 30, preferably Contain 8 to 16 carbon atoms. The alkyl group is preferably branched and unsubstituted. Particularly preferred are alkylbenzenesulfonic acids in which the alkyl group is unsubstituted, z. B. dodecylbenzenesulfonic acid. These additives can be produced by known methods.

The ethoxylated polymeric acid is made by reacting a polyalkylene glycol with a polymer Carboxylic acid produced. Suitable carboxylic acids are those having 14 to 60 carbon atoms each Carboxyl group; preferred acids are dilinoleic acid and trilinoleic acid. For the production of the ethoxylated polymeric acid is a mixture of polymerized fatty acids with a predominant one Trilinoleic acid content very suitable. Such acids fall as by-products in the form of distillation residues in the production of sebacic acid by distilling castor oil. The residue is an amber-colored, viscous substance, the long-chain one Contains polycarboxylic acids, an acid number between 140 and 165 and an iodine number between 30 and 60 and consists of the non-volatile fraction that is present in the vacuum distillation of the Production of sebacic acid from castor oil in the presence of alkali as a by-product Acids at 270 C and 4 mm Hg remains. These substances are in U.S. Patents 2,471,230, 2,267,269 and 2,470,849.

This distillation residue consists of monomers, dimers, trimers and higher polymers and is about 45 to 55 percent by weight of a monomer and dimer fraction of molecular weight from about 300 to 600 and about 55 to 45 weight percent from a higher fraction of polymer composed with a molecular weight above 600.

This residue becomes the additional component used according to the invention with a polyalkylene glycol implemented. Polyethylene glycol is preferred; however, polyglycols are suitable which consist of Alkylene compounds having 2 to 7 carbon atoms are made. The polyalkylene glycol is said to be a Molecular weight from 200 to 800, preferably from 300 to 500, have.

The polymeric carboxylic acid is present with the polyalkylene glycol in stoichiometric amounts an alkaline catalyst, e.g. B. of anhydrous sodium carbonate, sodium hydroxide Od. The like. Reacted, the catalyst being added in amounts of about 0.2 to 0.4 percent by weight will. The catalyst should be added after the temperature of the reactants

7 8

has been increased rapidly to about 150 C. Contained by weight percentage, the latter being the latter

the addition of the catalyst can add up to 30 to 90 percent by weight of the reaction combination,

participants further heated to about 260 ° C and 2 to preferably 45 to 75 percent by weight, from the

Maintained at this temperature for 4 hours. Sulfonic acid.

According to a preferred embodiment of _{FIG. 5,} if the additive mixture also contains deposits on the intake valves before the invention, the mixture described above can be a solvent oil in order to reduce the amount of deposits in a solvent oil such as that in Table I in the intake line. described, solve. The final gasoline mixture This oil should boil at 10 mm Hg in the range of 177, and the solvent oil should boil in amounts from 0.1 to 1 to 427 ° C, preferably from 204 to 371 ° C. _Io contain preferably 0.5 volume percent, by which the oil is intended to have on the intake valves at 98.9 ° C a viscosity of about 45 to 150 SUS formation of deposits. Typical characteristic values for the suppress.

Thinner oils are the following: Sometimes it is useful to replace the in

Table I described aliphatic solvent

Table I _{I5 e} j _n solvent to be used, which is at least

Specific weight 0.8827 ™ 50% from aromatics, ζ. B. toluene. the

Sulfur percent by weight 0.40 aromatic solvents suppress the

Neutralization number according to ^dun S ^of deposits is not as effective

ASTM D-974 0 02 manner; that in motor fuel according to the

Anilinounkt ⁰ C 134 ' ₂ o finding contained additive mixture is in

ASTM distillation is more resistant to aromatic solvents

Beginning of boiling ⁰ C 178 Additive mixture can be more easily dissolved in gasoline,

lOo / o-DestUlatpimi '»C'. '.'. '.'. '.".'. '. 240 ^we _t ⁿ " ^e * f * _t ^already * ^Lö ? ^un /% ^a , ^SOLUTION S ^s "

<cno / r> t-ii <■ w ° r · o7o is found to be the use of a

οπό / η! η ι? ^ ΪΓ »r« η * 5 aromatic solvent as advantageous if

900 / o distillate point, C 330 _{the solution of the additional mixture before its addition}

bieaeenae, <- · · · ■ J ° »must be stored _{to the gasoline} i _än g _he s time.

VerJcoKungsrucKstana Forms _{in solutions in} aromatic solvents

Conradson weight _{percent, no} ^S _Niecie rschlag 0.1 ■ while in solutions in

Saybolt viscosity at 98.9 C, aliphatic solvents a certain lower

• Seconds 60.7 3 _sc £ _{ag formation is observed} .

The condensation product of the imidazoline The motor fuel of the invention can and the alkenyl succinic anhydride is added to the still other additives, such as lead alkyls as anti gasoline in a small, to reduce the knock agents, anti-icing agents such as hexylene formation of deposits in the engine sufficient ₃₅ glycol, or other known fuel additives amount added. The amount required is included.

according to the respective gasoline, the presence the following additives are made: other additives etc., however, lies in general

in the range from 2.86 to 1430, preferably 43 Additive A

up to 286 g / m ³ gasoline. ₄ o j _Q ^ j

The combination of benzenesulfonic acid and

Ethoxylated dimeric acid is converted into an alkenyl succinic anhydride following the gasoline small amount added, which is sufficient, made to measure:

to achieve a practically complete separation in water of 2700 g of polyisobutylene (Staudinger molecular

and to effect gasoline. This amount is based on 45 weight 1100) are 270 g in a flask

according to the type of water sediment in question. Maleic anhydride added. The reaction part

The combination is supposed to be heated to 252 ° C for 19 hours with the gasoline in a concierge.

Tration of 10 to 120 parts per million added then ^{cooled to 6O 0} C, with 50 weight percent

will. You can also use larger amounts; Toluene, based on the total weight of the reac

however, this is usually not necessary. The pre-50 participants, diluted and filtered through a filter

Auxiliary filtered area for most purposes. The toluene is left overnight

is 25 to 40 parts per million. evaporated on the steam bath. It is only used for

The combination of benzenesulfonic acid and lowering the viscosity of the reaction product,

Ethoxylated dimeric acid can be used in different so that this can be filtered more easily. As a react

Quantities are applied. The benzene 55 ionization product gives a sticky, amber-

sulfonic acid should be 30 to 90 percent by weight, preferred colored mass with a saponification number of 67.2 mg

wise 45 to 75 percent by weight of the combination KOH / g.

be. _{Part 2}

The condensation product of imidazoline and

Alkenyl succinic anhydride, the benzenesulfonic. 60 An imidazoline is made as follows:

acid and the ethoxylated dimer acid are viscous- 300 g (5 mol) of glacial acetic acid are in a flask

liquid substances and can be added to 945 g (5 mol) of tetraethylene pentamine and 125 g

Gasoline added at about 54 to 66 "C to a practically xylene. The flask contents are at atmo-

homogeneous mixture are mixed together. Spherical pressure heated to reflux temperature and

This mixture is said to be the condensation product 65, the water of reaction in a receiver according to Dean

in amounts of 90 to 95 percent by weight and the and Stark collected until there is 152g of water

Combination of benzenesulfonic acid and ethoxy- have accumulated. The reflux treatment lasts

lated dimeric acid in amounts of 10 to 5 hours for 16 hours. After cooling the product will

the xylene used as a water entrainer by introducing nitrogen with heating on the Steam bath driven off. The imidazoline obtained is a dark yellow oil.

part 3

The alkenyl succinic anhydride is reacted with the imidazoline as follows:

50.2 g of the imidazolines prepared in accordance with Part 2 were mixed with 300 g of alkenyl succinic anhydride prepared in Part 1 in the presence of 70 g of toluene, 8 hours to 123 ⁰ C heated up in a template according to Dean and Stark 5 ml of water are collected. The toluene used as a water entrainer is then driven off by introducing nitrogen while heating on the steam bath. The end product is a dark, viscous material with a reddish tinge.

Addendum B

In the following experiments, technical grade dodecylbenzenesulfonic acid is used as additive B.

Addition C

The ethoxylated dimer acid preferred according to the invention is obtained by reacting polyethylene glycol (Molecular weight 400) with one according to US Pat. No. 2,471,230 (in particular Column 1, line 46, to column 2, line 10) produced distillation residue obtained; see. also U.S. Patent 2,723,233 which describes the use of this material.

66.93 g of distillation residue (molecular weight about 1200) and 33.07 g of polyethylene glycol (molecular weight 400) are mixed in a flask and air is passed through the mixture. After rapid heating to 149 ° C., 0.025 percent by weight anhydrous sodium carbonate is added. The reactants are then ^{heated to 260 °} C. and kept at this temperature for 2 ^{1 2 hours.}

The additives described above are tested in a gasoline which has the following characteristics Has:

Table II
Characteristic values of gasoline

Distillation according to ASTM D-86

20% distillate point, ⁰ C 55

55% distillate point, C 100

96% distillate point, C 180

End of boiling, ⁰ C 201.5

FIA analysis
saturated hydrocarbons,

Volume percentage -50

Olefins, volume percent 28.8

Aromatics, volume percent 21.2

Tetraethyl lead, cm ³ / 3.785 1 1.22

Research Octane Number 94.3

Engine octane number 84.8

example 1

4.5 ml of alkaline water sediment are added to 450 ml of the gasoline according to Table II. The mixture is stirred in a Waring mixer at 3600 rpm for 1 minute. Forms in the gasoline a water cloudiness; however, the water separates from that soon after the stirring is stopped Petrol.

Example 2

A solution is prepared from 1 g of additive A in 100 ml of toluene. For several 450 ml samples of the gasoline according to Table II are each 4.5 ml of alkaline water sediment and various amounts added to the solution of additive A in toluene.

The samples are stirred in a Waring mixer according to Example 1. One forms in the gasoline constant water turbidity. Most samples clear again after 6 hours; the excreted However, water contains gasoline and various amounts of the additive A. It also forms by moving it slightly (as would be expected with normal storage and transfer of gasoline is) immediately a constant water cloudiness in the gasoline again.

So it can be seen that Additive A (an effective multipurpose additive) encourages the formation of persistent Favors water cloudiness in gasoline and that part of the additive is lost from the gasoline, because an emulsion is formed from the additive A and the gasoline in water.

Example 3

There are samples of 450 ml of the gasoline according to Table II, 4.5 ml of alkaline water sediment, Additive A (0.27 g / l) and additive B (dodecylbenzenesulfonic acid in various concentrations in solution in toluene). The samples are stirred as described in Example 1. Most Samples clear again within 6 hours; at the interface between the gasoline and the However, water remains an emulsion of gasoline and additive A in water. It also forms when moving gently, as in example 2, again a constant water turbidity in the gasoline, which only slowly disappears. The addition B by itself hardly favors the complete one Separation into gasoline and water.

Example 4

Samples of 450 ml of gasoline each containing 4.5 ml of alkaline water sediment, a solution of additive A in toluene (258 g / m ³ ) and various amounts of additive C are prepared. All samples are stirred according to Example 1.

Most samples clear again after about 6 hours; however, remains at the interface an emulsion. In addition, when the samples are moved gently, the samples become cloudy again Petrol.

The above examples show that Additive A (an effective multi-purpose additive) can produce a Causes turbidity in the gasoline and the formation of an emulsion of gasoline and additive in water favored. The examples also show that neither the additive B nor the additive C on its own overcomes this difficulty. The following example explains the effectiveness of the additional combination according to the invention.

Example 5
65

Several gasoline samples (similar to the gasoline shown in Table II) are prepared, which are as follows Contain ingredients. The oil will dissolve

809 567/458

Claims (6)

11 12 of the ingredients before mixing with the gasoline emulsion at the interface and the mild beverage. . Movement of the samples does not lead to the formation of a Parts by weight of constant haze. The water spreads out " _A. - » _n - in the gasoline, but it finds an immediate separation Addition A 23.03. . Addition B 1.59 ^{5 statL} Addition C 0.64 claims: Solvent according to Table I .. 74.74 _{L of motor fuel with a content of} This additive mixture is a reaction product from a long of in varying amounts 0.875 to 0.2 g per sample for gasoline samples of 10 chain alkenyl succinic anhydride and one 450 ml each was added, the 4.5 ml alkaline water-organic nitrogen compound each as sludge sediment contain. inhibitor, characterized The samples are placed in the Waring mixer for 1 minute so that it is a mixture
at 3600 rpm. The samples become within 6 hours (some 15 a) a condensation product of a within 1 hour) clear. In contrast to the alkenyl succinic anhydride and a In the results of Examples 2 to 4, no imidazoline of the formula is formed: HR 'HH
RC = CCCH H-C-H N- (CH ₂ ) "- ENH (CH ₂ )" j
C. (CH ₂ ) ". -N jsr R " in which R and R 'denote hydrogen atoms or hydrocarbon radicals, but at least one of the two radicals is a hydrocarbon radical, and the total number of carbon atoms in the radicals R and R' is 40 to 250, while R "is an aliphatic hydrocarbon radical having 1 to 30 carbon atoms, η is a number from 2 to 3 and m is a number from 0 to 10, b) an alkylbenzenesulfonic acid, its alkyl group Has 1 to 30 carbon atoms, and c) a reaction product of a polyalkylene glycol having 14 to 60 carbon atoms per carboxyl group-containing polymeric carboxylic acid and optionally a solvent oil contains. 2. Motor fuel according to claim 1, characterized in that the contained therein Additive mixture of 90 to 95 percent by weight from the condensation product of imidazoline and Alkenylsuccinic anhydride and up to 10 to weight percent from the mixture of the Alkylbenzenesulfonic acid and the reaction product of polyalkylene glycol and polymeric carboxylic acid consists. 3. Motor fuel according to claim 1 or 2, characterized in that in the contained therein Additive mixture is the mixture of the alkylbenzenesulfonic acid and the reaction product from the polyalkylene glycol and the polymeric carboxylic acid, the alkylbenzenesulfonic acid Contains in amounts of 30 to 90 percent by weight. 4. Motor fuel according to claim 1 to 3, characterized in that in the contained therein Additive mixture the alkylbenzenesulfonic acid is dodecylbenzenesulfonic acid. 5. Motor fuel according to claim 1, characterized in that the contained therein Solvent oil is an aliphatic or aromatic oil. 6. Motor fuel according to claim 1 to 5, characterized in that it contains the additive mixture in such a concentration that the content of the condensation product of imidazoline and alkenylsuccinic anhydride 2.86 to 1430 g / m ^{3 of} fuel and the content of the mixture from the Alkylbenzenesulfonic acid and the reaction product of the polyalkylene glycol and the polymeric carboxylic acid is 10 to 120 parts per million parts of fuel. Considered publications:
French Patent No. 1,310,848; U.S. Patent Nos. 2,371,333, 2,334,239, 700,022, 2,296,069, 2,316,739, 3,115,397, 3,018,247, 018 250, 3 018 291. 809 567/458 6.6S Q Bundesdruckerei Berlin