DE1545502B2 - New salts of acidic alkyl phosphates with alkanolamines, their manufacture and their use as fuel additives - Google Patents

Description

(A) RR'N - CH ₂ CH (OH) CH ₂ OH

or

The invention relates to new salts of acidic alkyl- (g) R "N (R '") ₂

phosphates with alkanolamines, their production 55

and their use as fuel additives. in which R and R 'are hydrogen, alkyl, cycloalkyl, Phe-

In the operation of engines with internal Vernyl or Alkylphenyl with the proviso that combustion is often throttled or "stalled" that R and R 'together have 8 to 24 carbon atoms in the machine in climatic areas that have R " Alkyl, cycloalkyl, phenyl or a high humidity at temperatures between 60 aralkyl with 6 to 25 carbon atoms each and about 0 and 15 ° C. This throttling or R '"stifling a hydroxyethyl or hydroxypropyl radical is a side effect of the carburetor failure. interpret, where, if R "is an alkyl radical, such alkyl formation, which is excluded in particular on the throttle valve and groups, which occurs in the general direction of adjacent carburetor walls
gas freezing known formation of ice in the 65 R ₁

gas goes to the falling temperature of the metal \ ρττ

the carburetor parts when the fuel runs out /

steams. The low temperature of the metal reduces R ₂

3. '■■. /'.; 4. ... ■■■■ - ■■■■

have, in which R _{1 is} a straight-chain alkyl radical branched alkanols are preferably those which

with 1 to 3 carbon atoms and R ₂ a straight after the known oxo process from CO, H ₂ and

chain alkyl radical with 5 to 22 carbon atoms branched olefin, such as a C ₇ -C ₁₅ -monoole-

indicates. Finnish polymers and interpolymers of propylene The new salts are prepared by adding min- 5 and butylene, for example according to the USA.

at least one acidic primary alkyl orthophosphate, in which documents 2,824,836 and 2,884,379 have been obtained

the ester-forming alkyl groups are 8 to 16 carbon. Examples of preferred oxo alcohols for the

containing atoms, with an equimolar amount of a find are isooctyl alcohol from a propylene

Alkanolamine of the general formula butylene dimers, branched tridecyl primary alcohols

υ ρ'XT ru rwriH ^ HnH ^{10 made of triisobut} y ^{len and} tetrapropylene and branched

KKN-CH ₂ -CH (UtIJCH ₂ UH hexadecyl-primary alcohols from pentapropylene. Others

^or \ μώ '"\ branched-chain primary alcohols which, according to the

K-JN (KJ ₂ invention can be used by

wherein the radicals R, R ', R "and R'" represent the alkaline condensation of two primary alkanols in claim 1

have given meaning, are obtained in per se known 15 with the structure RCH ₂ CH ₂ OH,

Way. where R is an alkyl radical with 2 to 6 carbon

According to the invention, the new compounds are meant to be atoms. Primary alkanols are obtained as an additive for fuel mixtures on the basis of which are branched in the 2-position, for example hydrocarbon RCH ₂ CH ₂ CHRCh ₂ OH which is liquid under normal conditions. So z. B. 2-Hexylstoffdistillaten used. 20 decanol-1 by heating n-octanol with caustic

The amine salts of the present invention have schem and zinc dust and correspondingly 2-ethylhexa-

essentially neutral pH. The obtained according to the nol-1 from butanol-1, as described in detail in

Invention particularly preferred salt is the bis (2-hy- is described in the USA. Patent 2,457,866.

droxyäthyl) -n-dodecylamine salt of an approximately equimolar Other alcohols obtained after this process and after

Mixture of di-oxo-tridecyl hydrogen phosphate and 25 other known processes can be obtained

Mono-oxo-tridecyl dihydrogen phosphate, which is also called NEN and which is used in the context of the invention for production

C ₁₂ alkyl diethanolamine salt of the mixed acidic phosphates can be used

Mono- and di-tridecyl phosphate is called. those of the general formula

Other preferred salts of the invention are that ρ _Γ ττ _Γυ ητη> ηυ nu

.., "-,. , j ° ,. yy. r . . KCH ₂ CH ₂ - CHK - CH ₂ UH

N- (2,3-di-hydroxypropyl) -tert-dodecylamine salt of a 30th

approximately equimolar mixture of di-oxo-tridecyl- in which the two elements R are the same or different hydrogen phosphate and mono-oxo-tridecyldihydrogen-alkyl radicals, each with 2 to 6 carbon atoms, phosphate, the bis (2-hydroxyethyl) cocosamine salt of the branched alcohols can also be obtained by means of an approximately equimolar mixture of di-oxo-octyl-hydro- aldolization of suitable aldehydes with hydrogenation which includes phosphate and mono-oxo-octyl-dihydrogen phosphate. In this phat and the bis- (2-hydroxyethyl) coconut salt manner, the well-known oxooctaldehyde, which is obtained from an approximately equimolar mixture of di-oxo-tri-heptene-1, CO and H ₂ and essentially decyl hydrogen phosphate and mono -oxo-tridecyl-di- borrowed from a mixture of dimethylhexaldehydes, hydrogen phosphate. Ethylhexaldehydes and methylheptaldehydes with

The acidic primary alkyl ester of orthophosphoric acid 40 of the group —CH ₂ CH = 0 consists, in "2-hexylde- (acidic phosphates) are those esters in which only 1 or canol", R'CHRCH ₂ 0H is converted, with RC ₈ -Al-

2 of the three acidic hydrogen atoms of the orthophoskyl radicals, such as dimethylbutyl, methylpentyl and ethyl phosphoric acid have been replaced by alkyl radicals, such as. butyl radicals and R'Cg-alkyl radicals, such as the dimethylhexyl, the monoalkyl dihydrogen phosphates and the dialkyl, ethylhexyl and trimethylpentyl radicals. the hydrogen phosphates. These esters can after 45 straight-chain primary alkanols are easy to buy known methods are produced, e.g. B. available through. Examples of such straight-chain alcohols Reaction of an alcohol with phosphorus pentoxide. are octanol, nonanol, decanol, dodecanol, tri-approximately 2 to about 4 mol of the alcohol can be used per mol of decanol, tetradecanol and hexadecanol.

P ₂ O ₅ can be used. Preferably, the acidic alkyl preferred according to the invention

3 moles of the alcohol are used per mole of P ₂ O ₅ , with a 5 ° phosphate being the acidic mono- and dialkyl phosphates, approximately an equimolar mixture of the mono- and dialkyl phates in which the alkyl radicals are the isooetyl and 2-ethyl esters of orthophosphoric acid. The hexyl, the tridecyl and / or the hexadecyl radical mixed contains about 40 to about 60 mol percent of the mean.

Monoalkyl ester and the remainder the dialkyl ester. These The amines, which according to the invention for the win-

Mixtures of mono- and dialkyl esters are used for reasons of the new salts of acidic alkyl phosphates preferred for economy. In the context of sets, the two specified are different However, other mixtures and classes of alkanolamines can also be used according to the invention.

likewise the monoalkyl esters or the dialkyl esters as The first class designated with (A) has the appropriate

Individual compounds used for amine salt formation given general formula:
will. The esters can be made from their 60

Mixtures produced by known (A) RR'N - CH ₂ CH - CH ₂

Methods are separated. Il

The for the production of the acidic primary alkylphos OH OH

Phate alcohols used are straight-chain or

branched primary alkanols with 8 to 16 carbon atoms, where R and R 'are hydrogen, alkyl, cycloalkyl, and phosphate atoms or mixtures of two or more straight nyl or alkylphenyl, where the total number chain or branched alcohols or mixtures of the carbon atoms in the radicals R and R '8 to 24 of straight-chain and branched alkanols. That amounts to. Important examples of the alkyl and cyclo-

5 6

alkyl radicals are ethyl, butyl, hexyl, n-octyl, enable easy handling of the salts and tert-octyl, n-dodecyl, tert-dodecyl and hexa facilitate mixing in the base gasoline , decyl radical and the mixed C ₁₈ - to C ^ -terk-alkyl- In the following examples all quantitative fractions are cyclohexyl, cyclooctyl and cyclodecyl. gave as amounts by weight, as far as examples of the alkylphenyl radicals are p-octylphenyl,. 5 is not expressly stated otherwise. p-decylphenyl and p-dodecylphenyl. The alkanolamines of this class can be prepared in any manner known from the prior art. So they can produce the alkanolamine phosphate salt z. B. easily by reacting the appropriate amine. _TT ^ ",. ",,, RR'NH with S-chloropropanediol-l ^ io A. Preparation of the acidic alkyl phosphate

[Ci-CH ₂ -CH (OH) -CH ₂ OH] 142 g (l mol) of Phosphoipentoxyd are proportionally

^{1 2 v} ' ^{2 J} successively in 60Og (3MoI) oxo-tndecyl alcohol

can be obtained. Stir in the preferred amines of this class. While adding P ₂ O ₅ one leaves

are those amines in which R is hydrogen and R 'one increases the temperature to about 65 ^° C. The Rea-

n-Dodecyl-, tert-Dodecyl- or tert-Cig-Cag-Alkyl- 15 tion mass is then at about 65 ° C by external

mean rest or both R and R 'are butyl radicals. Kept cool. After the P ₂ O _{5 has been} added

The second class of earth, labeled (B), is the reaction mass at temperature

Amines used according to the invention correspond to the total of about 65 ° C., stirred for a further 12 hours.

common formula

_2o B. Neutralization of the acidic phosphate with the

(B) R "N (R '") ₂ amine component

in which R "is an alkyl, cycloalkyl, phenyl or N- (2,3-dihydroxypropyl) -tert-dodecylamine, i.e.

Aralkyl hydrocarbon radical with 6 to 25 carbons tert-dodecyl-NH-CHaCHOHCH-jOH, is in a

substance means atoms. Examples are the octyl, amount of 518 g (2MoI) dropwise according to Isooctyl, decyl, dodecyl, tridecyl, tetradecyl, 25 A prepared reaction mixture added, the

Hexadecyl and octadecyl radical and mixed C _{8 to} temperature between 60 and 70 ° C is maintained.

C ₁₆ alkyl fractions of. Cocosamine, Cyclohexyl, The mixture is heated for a few hours at 60 to 70 ° C

Cyclodecyl, Cyclooctadecyl, Phenyl or Octylbenzyl, stirred and thereby the mixing and neutralization

Hexylbenzyl, decylbenzyl and octadecylbenzyl. The formation reaction is completed is either a hydroxyethyl or a hydroxy 30 N- (2,3-dihydroxypropyl) -tert.-dodecylamine salt of a

propyl radical. This class of alkanolamines can be approximately equimolar mixtures of di-oxo-tridecyl-

easily by reacting 1 mole of the appropriate hydrogen phosphate and mono-oxo-tridecyl-dihydro-

Amine R "NH ₂ with 2 moles of ethylene oxide or propylene phosphate.

oxide can be obtained. Another way for the profit- The reaction mass is with kerosene too tion of this class of amines, where. R '"the Hy- 35 of an approximately 80 percent by weight solution of the

means droxyäthylrest, the conversion of alkylths neutralized product is added. Instead of

or aralkyl chlorides R "C1 with diethanolamine of the light petroleum can also be a lower alcohol,

[HN (CH ₂ CH ₂ OH) ₂ ]. In the case of the preferred amines, for example methanol, used as a diluent

This class means R "n-dodecyl, octadecyl, cyclo- sets to be a highly flowable additive for hexyl or octadecylbenzyl or residues that can be obtained from natural distillate fuels,

borrowed fatty acids with 8 to 18 carbons- After another method for the production of the

Substance atoms such as coconut oil have been extracted. The amine can be used as an amine salt in the neutralization stage

The use according to the invention of the new used dissolved in kerosene or methanol

Compounds will be the properties of distillate, said salt being directly fueled as free vastly improved. 45 possible solution of z. B. 80 percent by weight in

Is obtained in the solvent by the use according to the invention.

Improved distillate fuels is the amount of Da the process of making the acidic alkyl alkanolamine salts from alkyl ester phosphates, the phosphate to a mixture of mono- and dihydrodem When gasoline is added, which leads to crucial hydrogen phosphates, it is of far importance in practice, as long as the amount added is sufficient to add 50, use this mixture in the preparation of the amine salts To use gasoline with regard to the property of the undesirable. The resulting alkanolamine salt mixture To improve throttling. When adding to gasoline, it can then be used directly as a gasoline additive, Salt amounts of from about 0.0003 to about 0.02 are used. However, if specific alkanolamine salts according to the weight percent - based on the weight of the Destil invention instead of the mixtures are desired, lat fuel - preferred. The gasoline mixtures can then be obtained by In addition to the alkanolamine phosphate salts, all initially include the monohydrogen phosphate from the di-additives which separates hydrogen phosphate incorporated into modern gasoline and then isolates it will. Examples of such additives are anti- acidic phosphates with a certain alkanol knocking agent, Reacts antioxidants, dyes and metal amines. The separation of the monohydrate deactivators, the behavior of the drug phosphates according to the invention 60 from the dihydrogen phosphates Do not adversely affect added salts and is carried out in a manner known per se. So can the addition according to the invention in gasoline is compatible, for example, with di-oxo-tridecyl hydrogen phosphate are. For the use of the salts as a means against separated from the mono-oxo-tridecyl hydrogen phosphate unwanted throttling in gasoline, it will be preferred and won, as it is in the USA. the salts in a solvent such as methanol is described in 65 documents 2,818,421 and 2,854,468. That Luminous kerosene or xylene, separated in sufficient quantities by di-oxo-tridecyl hydrogen phosphate to dissolve concentrations to 50 to 80 weight percent then with N- (2,3-dihydroxypropyl) -tert-dodecylamine to produce concentrated salt solutions. Such concentrates are implemented and the corresponding amine salt is

which is free of substantial amounts of the dihydrogen phosphate amine salt. The amine salt of the dihydrogen phosphate is used in a corresponding manner by reacting mono-oxo-tridecyl dihydrogen phosphate with N- (2,3-dihydroxypropyl) -tert-dodecylamine won.

The measures according to A and B of this example are substituted with other dihydroxyl-alkyl Amines and other acidic alkyl phosphates repeated as indicated in Table I below, corresponding salts being produced as additives according to the invention.

'Table I.

Dihydroxyalkyl amine salt components

H Alkanolamine Acid
Phosphates *) (A) RR'l
R. H ^ -CH ₂ -CH (OH) CH ₂ OH
R ' Tridecyl **) H tert-dodecyl Tridecyl Cyclohexyl 2,4-dimethylphenyl Tridecyl H n-dodecyl Tridecyl ethyl Cyclohexyl Tridecyl H p-dodecylphenyl Tridecyl Cyclohexyl ethyl mixed tert-C ₁₈ - bis Tridecyl n-butyl C ₂₄ alkyl fraction Tridecyl H Phenyl Tridecyl H n-butyl Isooctyl **) tert-dodecyl Hexadecyl tert-dodecyl

Table I still

Alkanolamine Acid
Phosphates *) R " (B) R "N (R '") ₂
R "' Tridecyl n-dodecyl CH ₂ CH ₂ OH Tridecyl Phenyl CH ₂ CH ₂ OH Tridecyl n-octadecyl CH ₂ CH ₂ OH Tridecyl Tall alkyl CH ₂ CH ₂ OH n-octa- CH ₂ CH ₂ OH decylbene Tridecyl cyl Tridecyl Cyclohexyl CH ₂ CH ₂ OH n-dodecyl CH ₂ CH ₂ OH Tridecyl benzyl Isodecyl n-dodecyl CH ₂ CH ₂ OH Isooctyl Coconut alkyl CH ₂ CH ₂ OH mixed Coconut alkyl CH ₂ CH ₂ OH C ₁₂ bis C ₁₆ alkyl fraction Di- (2-ethyl- Coconut alkyl CH ₂ CH ₂ OH hexyl) Hexadecyl Coconut alkyl CH ₂ CH ₂ OH Tridecyl Coconut alkyl CH ₂ CH ₂ OH Tridecyl Cyclohexyl CH ₂ CH (CH ₃ ) OH Tridecyl Phenyl CH ₂ CH (CH ₃ ) OH Tridecyl n-dodecyl CH ₂ CH (CH ₃ ) OH n-dodecyl CH ₂ CH (CH ₃ ) OH Tridecyl benzyl

*) Unless otherwise stated, a mixture of the mono-diester.

· *) The data tridecyl and isooctyl in this table refer to refer to the groups present in oxo-tridecyl and oxo-octyl alcohols.

B e i s ρ i e 1 Ii

Gasoline samples are prepared containing alkanolamine phosphate salts according to the invention and tested in an internal combustion engine. The tests are used to determine the effect of the additives according to the invention on the gasoline properties with regard to carburetor icing and carburetor contamination carried out. The samples are prepared by taking small amounts of the respective Alkanolamine phosphate salts are added to gasoline; for details see Tables II, III and IV.

The gasoline used in the tests is a commercially available product and has the following properties:

'Reid vapor pressure ....... 0.91 kg / cm ²

ASTM distillation (D86) ⁰ C

Initial boiling point 24

10 ° / o 40

^ao 50% 90

90% 170

End boiling point ..208

The following is a brief description of the Testas conditions and the devices that are used Determination of the samples have been used.

Prevention of ice formation

The influence of the alkanolamine phosphate salts according to the invention on the stalling of the engine is determined in a 6-cylinder Chevrolet engine with 86 hp at 3400 rpm and a stroke of 3548 cm ³ . Two different types of carburetors are used, namely (a) a throttle valve carburetor and (b) a mixed tube carburetor. The experimental conditions are as follows:

Intake air, ⁰ C

relative humidity, %

Engine load in PS .......

Motor speed, rpm

Idle speed,
RPM

Fuel temperature
to the carburetor in ° C.

Carburetor type

throttle

3 to 5
98 to 100

10

1500 at ho-1500
here fast
speed

, 350
10 to 13

Mixing tube

1 to 2

98 to 100

15th

initially

10 to 13

(a) Throttle valve carburetor

The operating time of the engine is varied under the specified conditions; which it took to stall Time is taken as a measure of the fuel: that caused by carburetor icing : To cause or prevent stalling. All Attempts are made after having previously opened the carburetor flap at a temperature of 5 ° C for has been treated with methanol for 0.5 minutes. The operating time used for the The engine depends on the tendency of the fuel to form ice. The operating times for an engine

309544/532

ίο

speeds of 1500 rpm are typically in the range of 0.5 to 1.5 minutes for uninhibited Base fuels. At the end of the 1500 RPM duty cycle, the throttle will turn back on pushed back to the idle position. If no stalling within 30 seconds when idling occurs, the experiment is repeated with a longer period at 1500 rpm, until an operating time is found at which the engine will run within 30 seconds of restarting idling is stalled. As a comparative figure for the property of gasoline to be determined here the longest operating period at 1500 rpm (based on the closest 0.25-minute segment), followed by a full 30 second idle period with no engine stalling. The measure of 3 or more minutes is rated as excellent performance in the test.

(b) Mixing tube carburetor

A Solex downdraft carburetor model No. 32 PBICA is used in place of the previously described throttle valve carburetor and then the engine under the operated under the same conditions. Under these conditions and using the mixed tube carburetor the engine will not stall completely. Rather, the engine will run for 20 minutes at an initial speed operated at 1500 rpm and the reduction in motor speed taken as a measure of the effectiveness of the anti-icing agent. One Reduction of not more than 50 rpm within the operating time of 20 minutes is considered an excellent one Rated anti-ice behavior.

To demonstrate the effectiveness of the additives according to the invention, benzines free of these salts are used as well as gasolines mixed with these salts according to the invention were tested. The experiments with the basic fuels without the addition according to the invention lead to a stall time of 0.25 minutes

ίο Working with the throttle valve carburetor or too a reduction in engine speed to 900 RPM after 20 minutes of operating time while working with the mixing tube carburetor. The results from experiments in which the gasoline used alkanolamine salts

»5 measured the invention contains in amounts that are against the The appearance of stalling are summarized in Table II below.

Regarding the unique property of the additives according to the invention when operating engines with

Ao mixing tube gasifiers to be able to prevent stalling at all, show the invention Alkanolamine salts also have great effectiveness over conventional throttle valve carburetors. It is in itself It is known that additives which are effective in one type of carburetor do not necessarily affect the affect others. For example, unsubstituted amine salts of acidic phosphates are known Anti-icing agent for use in throttle valve carburetors. In the type of mixer tube carburetor however, they have little effect or are completely ineffective.

Tables of attempts to prevent ice formation

Additive (80 weight percent solution
in kerosene)
(A) RRZN-CH ₂ -CH (OH) CH ₂ Oh ■ n H TJ / Sour Weight percent
of the additive
in fuel Throttle valves
carburetor
Stall time Mixing tube carburetor
Motor top speed
speed R. R. Phosphate*) in minutes tert-dodecyl Tridecyl RPM 0.002 3.00 H 0.004 1250 0.008 1400 H 2,4-dimethyl 0.012 1450 Cyclohexyl phenyl Tridecyl H n-dodecyl Tridecyl 0.006 1375 Cyclohexyl Tridecyl 0.006 3.00 ethyl p-dodecylphenyl Tridecyl 0.006 1400 H 0.004 2.75 Cyclohexyl Tridecyl. 0.012 1400 mixed tertiary Tridecyl 0.006 1400 ethyl C ₁₈ - to C ₂₄ -Al- 0.006 > 3.00 n-butyl kyl fraction 0.016 1300 Phenyl Tridecyl n-butyl Tridecyl 0.006 1000 H 0.003 3.00 0.004 > 3.00 H tert-dodecyl Isooctyl 0.004 1475 0.002 1200 tert-dodecyl Hexadecyl 0.004 1450 0.004 1150 0.016 1000

*) Unless otherwise stated, a mixture of the mono- and diesters.

Table II (continued)

Additive (80 weight percent solution
in kerosene)
(B) R "N (R '"), Tl // T> "/ Sour Weight percent
of the additive Throttle valve
Carburetor Mixing tube carburetor
Motor end speed R. ...... ^R Phosphate*) in fuel Stall time speed n-dodecyl CH ₂ CH ₂ OH Tridecyl in minutes RPM 0.001 1350 0.002 2.25 1475 Phenyl CH ₂ CH ₂ GH Tridecyl 0.003 3.00 n-octadecyl CH ₂ CH ₂ OH Tridecyl 0.004 1500 0.006 1150 Tall alkyl CH ₂ CH ₂ OH Tridecyl 0.004 1.00 n-octadecylhexyl CH ₂ CH ₂ OH Tridecyl 0.016 2.50 Cyclohexyl CH ₂ CH ₂ OH Tridecyl 0.008 1350 0.006 2.25 0.002 1375 n-dodecylbenzyl CH ₂ CH ₂ OH Tridecyl 0.004 1475 0.004 1475 0.004 1300 n-dodecyl CH ₂ CH ₂ OH Isodecyl 0.012 1430 Coconut alkyl CH ₂ CH ₂ OH Isooctyl 0.016 1500 0.006 1500 Gocosalkyl CH ₂ CH ₂ OH mixed C ₁₂ - 0.002 1375 up to C ₁₆ -Al- 0.004 1450 kyl fraction 0.004 1250 Coconut alkyl CH ₂ CH ₂ OH Di- (2-ethyl- 0.012 1450 hexyl) Coconut alkyl CH ₂ CH ₂ OH Hexadecyl 0.004 1300 Coconut alkyl CH ₂ CH ₂ OH Tridecyl 0.008 1475 Cyclohexyl CH ₂ CH (CH ₃ ) OH Tridecyl 0.002 1400 0.004 3.00 1500 0.001 1.25 n-dodecyl CH ₂ CH (CH ₃ ) OH Tridecyl 0.002 > 3.00 1400 0.004 .., ..: _. 1500 0.002 2.50 0.003 2.75 0.004 > 3.00 0.008 1500

*) Unless otherwise stated, a mixture of the mono- and diesters.

Table IH Attempts to Prevent Ice Formation

Phosphate*) Weight Mixed Tridecyl percent
of the additive pipe in fuel carburetor Isooctyl Engine-
end- Additive (80 percent by weight speed Solution in solvent) Isooctyl 0.004 age 0.008 RPM Isooctyl 0.004 900 Amine 0.008 900 2-ethylhexyl C ₈ - to C ₁₈ - 0.004 1150 Alkyls from 0.008 625 2-ethylhexyl Coconut oil 0.004 950 Di-2-ethyl 0.016 1150 N-tall-1,3-di- hexyl 0.004 1100 aminopropane 0.016 750 C ₁₂ - to C ₁₅ - 1150 tert-alkyl 0.004 775 Di-2-ethyl 0.016 hexyl 1025 • 950 Di-2-ethyl hexyl

*) Mixture of mono- and diesters, unless otherwise stated.

Comparative tests are made under the corresponding test conditions in order to show the effect of various unsubstituted amine phosphate salts on the phenomenon of engine stalling. The results are summarized in Table III.
It can be seen from Table III that a considerable decrease in the speed of rotation occurs if unsubstituted amine phosphates are used instead of the alkanolamine phosphates according to the invention according to Table II. In most cases, this effect will increase as the amount of additive increases

In addition, the alkanolamine salts according to the invention show a superior effect over the unsubstituted ones Amine salts in tests with conventional throttle valve carburetors. For example, Use of a commercially available gasoline with an average boiling point of 110 ° C as the base fuel a stall time of 3 minutes in the throttle valve carburetor is achieved if 0.008 percent by weight (80% active ingredients) of the 2-ethylhexylamine salt des acidic tridecyl phosphate can be used. From the n-dodecyl diethanol amine salt of acid tridecyl phosphate However, only 0.0016 percent by weight (80% active ingredients) are required to achieve the same stall

time of 3 minutes in the throttle valve carburetor.

The alkanolamine salts according to the invention also show an excellent cleaning effect on the carburetor. Even if only with one in the following test to determine this cleaning effect Throttle valve carburetor is used, this attempt can also be carried out on a mixing tube carburetor be applied.

Carburetor cleaning effect

The carburetor cleaning effect of the alkanolamine phosphate salts according to the invention can be applied to one Lausen test engine equipped with a Tillotsen carburetor, the removable leaflet having around the throttle valve. During the experiment, part of the exhaust gas is released from a second Single cylinder engine, which is operated at a constant speed of 2500 rpm, in the test Carburettor initiated. The test engine is run for 1 minute at a time for a period of 2 hours

open throttle under dynamometer load and then for 2 minutes at idle 1100 ± 100 rpm operated. After the end of the experiment, the leaflets are removed and placed in one of 1 to A 10-range scale, with the number 10 being a shiny, shiny one. Appearance and the number 0 mean very heavy black precipitation. The basic fuel of this experiment is the same the previous anti-ice tests. .--.

ίο The comparative consideration of the leaflets from a carburetor, after the engine was run on the basic gasoline, with leaves from one Carburetor after operating the engine with a gasoline that contains the additives according to the invention, shows the effective cleaning power of the additives according to the invention. The results of this comparative considerations are given in Table IV below. . . .

From this table it can be seen that high cleaning effects in the carburetor are already very low Quantities of the alkanolamine phosphate salts according to the invention can be achieved in the gasoline.

Table IV Cleaning Effect on the Carburetor

H R ' acidic phosphate *) Weight percent of the Determination of H tert-dodecyl Tridecyl Additive Cleaning effect mixed tert-C ₁₈ - to C _{24 -} Tridecyl in fuel ^: on the carburetor Base gasoline H Alkyl fraction 5.6 H n-dedecyl Tridecyl p-dodecylphenyl Tridecyl H Octadecyl Tridecyl 0.004 9.5 Additive (80 percent by weight solution in kerosene) Butyl 0.004 8.4 (A) RRTM-Ch ₂ -CH (OH) CH ₂ OH Butyl Tridecyl 0.006 9.0 R. 0.004 9.1 0.004 7.8 0.006 9.7 0.004 9.5 0.006 9.9 0.004 9.3 0.006 10.0

B) R "N (R '") _a R '" Table IV (continued) 0.004 9.0 ■ ' ^: ( CH ₂ CH ₈ OH 0.002 .9.3 R " CH ₂ CH ₈ OH 0.003 9.9 Octadecylbenzyl CH ₂ CH ₈ OH 0.004 9.2 n-dodecyl CH ₂ CH ₂ OH 0.004 9.8 Octadecyl CH ₈ CH (CH ₃ ) OH 0.006 : 8.0 Tall alkyl 0.008 9.8 Cyclohexyl CH ₂ CH (CH ₃ ) OH 0.012 9.6 n-dodecyl Tridecyl Tridecyl Tridecyl Tridecyl Tridecyl Tridecyl

*) Mixture of mono- and diesters of acid tridecyl phosphate.

Claims (3)

1 2. in turn causes the condensation of the patent claims with the air: moisture entering the carburetor, its water particles on the edge of the throttle valve and on 1. Ice salts of acidic primary alkyl orthophosphates in the air supply to the gasifier. The Eisin to which the esterifying alkyl radicals 8 to 16 carbon formation on the edge of the gasifier flap places the air carbon atoms included, with an equimolar inflow to the engine, which is thus throttled or Amount of alkanolamines of the general form is stifled. In addition, the formation of ice leads to the my air supply or venturi for stalling (A) RR'N CH CH (OHICH OH ^ ^es engine as a result of an excessively rich mixture. ^{2 2} ίο Such ice formation also takes place in the mixer or pipe carburetors, which are predominantly used in motor vehicles. (B) R "N (R '") £ ^{s of} foreign manufacture may be used. In ² such a mixing tube carburetor are air and in which R and R 'hydrogen, alkyl, cycloalkyl, fuel mixed, flow in a coordinated amount Phenyl or alkylphenyl with the proviso mean 15 from and are then gasified. The ice forms first that R and R 'together have 8 to 24 carbon at the inlet of the air correction nozzle of the mixing tube, atoms, R "is an alkyl, cycloalkyl, phenyl which leads to throttling or stalling of the engine. or aralkyl each having 6 to 25 carbon atoms. men and R '"a hydroxyethyl or hydroxy A frequent throttling of the engine is also possible propyl radical, where, if R "is an alkyl radical, 20 operating conditions are restored by high loads is, such alkyl groups are excluded that arise in traffic when stopping and starting up the general formula come when the engine often idles _{Ώ is} drifting. The engine stalling with such ! \ Traffic behavior is mainly due to the • CH - 25 storage of foreign materials on the walls of the ■ o / throttle body back, located below the ² closed throttle valve. Foreign matter have, in which R _{1 is} a straight chain alkyl can be in the carburetor at idle speed rest with 1 to 3 carbon atoms and R ₂ occur because the air filter in this case straight-chain alkyl radical with 5 to 22 carbon speeds is relatively ineffective. Most atoms means. Impurities or foreign matter particles that affect the 2. Method of making connections to reach carburetors at idle speeds, according to who Claim 1, characterized in that the from the engine through the crankcase ventilation blown out at least one acidic primary alkyl orthodontation. The impurities remain phosphate, in which the first forming alkyl groups 35 but included under the hood when the Contain 8 to 16 carbon atoms, with a carriage stopped, and may be used when the car is idling Equimolar amount of an alkanolamine of the all-engine easily enter the carburetor. Other sources The formulas for the impurities are the exhaust gases of the T? R '> j CVf rwnmrvf nw front car as well as the usual smoke and dust that in KK JN - CH ₂ - CH (UHJCH ₂ UH _{40 of the air as a result of} traffic conditions present ⁰ "> j / -p '" \ den ^smc *> which allows the operation of engines under high JS (K; ₂ require exposure. It is generally known wherein the radicals R, R ', R "and R'" can eliminate this source of error in that the Claim 1 have given meaning, in itself 'engine idling is increased, but this is so implemented in a known manner. 45 disadvantageous as the fuel consumption is increased. 3. Use of compounds according to An The invention relates to acidic salts Claim 1 as an additive for fuel mixture on the primary alkyl orthophosphates, in which the esterify base the alkyl radicals which are liquid under normal conditions contain 8 to 16 carbon atoms, Hydrocarbon distillates. with an equimolar amount of alkanolamines of 50 general formulas