DE1545502C3 - New salts of acidic alkyl phosphates with alkanolamines ^ their production and their use as fuel additives - Google Patents

Description

or

The invention relates to new salts of acidic alkyl phosphates with alkanolamines, their production and their use as fuel additives.

When operating engines with internal combustion, throttling or "stalling" often occurs of the machine in climatic areas with high humidity at temperatures between about 0 and 15 ° C. This throttling or stalling is a side effect of carburetor icing, which occurs in particular on the throttle valve and the adjacent carburetor walls. The carburetor icing known formation of ice in the carburetor is due to the falling temperature of the metallic Carburetor parts back when the fuel evaporates. The low temperature of the metal

(A) RR'N - CH ₂ CH (OH) CH ₂ OH

(B) R "N (R '") ₂

in which R and R 'are hydrogen, alkyl, cycloalkyl; Phenyl or alkylphenyl with the proviso that R and R 'together have 8 to 24Koh enstofiat , me , R "is an alkyl, cycloalkyl, phenyl or aralkyl with 6 to 25 carbon atoms and R'" is a hydroxyethyl or hydroxypropyl radical, where when R "is an alkyl radical, those alkyl groups are excluded which the general formula

Ri

rcH -

in which R _{1 is} a straight-chain alkyl radical having 1 to 3 carbon atoms and R _{2 is} a straight-chain alkyl radical having 5 to 22 carbon atoms.

The new salts are prepared by adding at least one acidic primary alkyl orthophosphate, in which the ester-forming alkyl groups contain from 8 to 16 carbon atoms, with an equimolar amount of one Alkanolamine of the general formula.

RR'N - CH ₂ - CH (OH) CH ₂ OH
R "- N (R '") ₂

wherein the radicals R, R ', R "and R'" are as described in claim 1 have given meaning, implemented in a manner known per se.

The new compounds are used according to the invention as an additive for fuel mixtures based on Hydrocarbon distillates that are liquid under normal conditions used.

The amine salts of the present invention are essentially neutral in pH. The particularly preferred salt according to the invention is the bis (2-hydroxyethyl) -n-dddecylamine salt of an approximately equimolar mixture of di-oxo-tridecyl hydrogen phosphate and mono-oxo-tridecyl dihydrogen phosphate, which is also known as the C ^ -alkyl diethanolamine salt of the mixed acidic mono - and Di-tridecylphosphate is called. Other preferred salts of the invention are the N- (2,3-di-hydroxypropyl) -tert-dodecylamine salt of an approximately equimolar mixture of di-oxo-tridecyl hydrogen phosphate and mono-oxo-tridecyl dihydrogen phosphate, the bis (2-hydroxyethyl) cocosamine salt of an approximately equimolar mixture of di-oxo-octyl hydrogen phosphate and mono-oxo-octyl dihydrogen phosphate and the bis (2-hydroxyethyl) ⁱ cocosamine salt of an approximately equimolar mixture of di-oxo-tridecyl hydrogen phosphate and mono-oxo tridecyl dihydrogen phosphate.

The acidic primary alkyl esters of orthophosphoric acid (acidic phosphates) are esters in which only 1 or

2 of the "three acidic hydrogen atoms of orthophosphoric acid have been replaced by alkyl radicals, such as the monoalkyl dihydrogen phosphates and the dialkyl hydrogen phosphates. These esters can be prepared by methods known per se, for example by reacting an alcohol with phosphorus pentoxide. About 2 to about 4 mol of the Alcohol can be used per mole of P ₂ O ₅ , preferably about

3 moles of the alcohol are used per mole of P ₂ O ₅ , an approximately equimolar mixture of the mono- and dialkyl esters of orthophosphoric acid being obtained. The mixture contains from about 40 to about 60 mole percent of the monoalkyl ester and the remainder the dialkyl ester. These mixtures of mono- and dialkyl esters are preferred for reasons of economy. In the context of the invention, however, other mixtures and also the monoalkyl esters or the dialkyl esters can be used as individual compounds for amine salt formation. The esters can be separated off from their mixtures obtained during production by methods known per se.

The alcohols used for the preparation of the acidic primary alkyl phosphates are straight-chain or branched primary alkanols with 8 to 16 carbon atoms or mixtures of two or more straight-chain or branched alcohols or mixtures of straight-chain and branched alkanols. The branched alkanols are preferably those obtained by the known oxo process from CO, H ₂ 'and a branched olefin, such as a C ₇ -C ₅ mono-olefinic polymer and interpolymers of propylene and butylene, for example in accordance with U.S. Patents 2,824,836 and 2,884,379. Examples of preferred oxo alcohols for the invention are isooctyl alcohol from a propylenebutylene dimer, branched tridecyl primary alcohols

ίο from triisobutylene and tetrapropylene and branched hexadecyl primary alcohols from pentapropylene. Other branched-chain primary alcohols which can be used according to the invention can be obtained by alkaline condensation of two primary alkanols with the structure RCH ₂ CH ₂ OH, where R here denotes an alkyl radical having 2 to 6 carbon atoms. This results in primary alkanols which are branched in the 2-position, for example according to RCH ₂ Ch ₂ CHRCH ₂ OH. So z. B. 2-hexyl-decan'ol-1 obtained by heating n-octanol with caustic and zinc dust and correspondingly 2-ethylhexanol-1 from butanol-t, as described in detail in the US Pat. No. 2,457,866. Other alcohols which can be obtained by this process and by other known processes and which can be used in the context of the invention for the preparation of the "phosphates" are those of the general formula

RCH ₂ CH ₂ -CHr-CH ₂ OH

in which the two elements R are identical or different alkyl radicals each having 2 to 6 carbon atoms. The branched alcohols can also be obtained by a customary aldolization of suitable aldehydes with subsequent hydrogenation. In this way, the well-known oxooctaldehyde, which is obtained from hepten-1, CO and H ₂ and consists essentially of a mixture of dimethylhexaldehydes, ethylhexaldehydes and methylheptaldehydes "with the group - CH ₂ CH = O, in» 2-hexylde- , canol ", R ⁷ CHRCH ₂ OH, where RC ₈ -alkyl radicals, such as dimethylbutyl, methylpentyl and ethylbutyl radicals, and R'Cj -alkyl radicals mean the dimethylhexyl, ethylhexyl and trimethylpentyl radicals. The straight-chain primary alkanols are easily available commercially. Examples of such straight-chain alcohols are octanol, nonanol, decanol, dodecanol, tridecanol, tetradecanol and hexadecariol.

The acidic alkyl phosphates preferred according to the invention are the acidic mono- and dialkyl phosphates in which the alkyl radicals are the isooctyl, 2-ethylhexyl, the tridecyl and / or the hexadecyl radical.
The amines, which according to the invention for the win-

tion of the new salts of the acidic alkyl phosphates are the indicated two different classes of alkanolamines ^

The first class labeled (A) has the specified general formula: ■

. . ■ '"- ■' ■ ■"^;

(A) RR ⁷ N-CH ₂ CH-CH ₂

• -. : ι- ι. . ■■■■ -. '■

OH OH

where R and R 'are hydrogen, alkyl, cycloalkyl, phenyl or alkylphenyl, where the total number of carbon atoms in the radicals R and R 'is 8 to 24 amounts to. Important examples of the alkyl and cyclo-

5 6.

alkyl radicals are the ethyl, butyl, hexyl, n-octyl, allow easy handling of the salts and

tert-octyl, n-dodecyl, tert-dodecyl and hexa- facilitate mixing in the base gasoline,

decyl radical as well as the mixed C ₁₈ - to C ^ -tert.-Alkyl- In the following examples all quantities are

fractions, cyclohexyl, cyclooctyl and cyclodecyl. gave as amounts of weight to be understood as far as it is

Examples of the alkylphenyl radicals are p-octylphenyl, 5 unless expressly stated otherwise.

p-decylphenyl and p-dodecylphenyl. The alkanol. ■ - ,. ■■; ■■■■. , -

Amines of this class can be applied to any of the examples I.-...-., ._

Technique known manner. So can manufacture of the alkanolamine phosphate salt -

she z. B. easily by reacting the appropriate amine. _TT ", '■■■"" ,, ■■■■■, - · .., · .-,"

RR'NH with 3-chloropropanediol-l, 2 io A. Production of the acidic alkyl phosphate,

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

^{1 in} succession in 600 g (3 mol) of 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-Cjg-Caü-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

invention employed in accordance with amines general stirred from about 65 ⁰ C for an additional 12 hours is equal.

common formula. . " _Xr,, . . , ", _L. , ·

₂₀ B. Neutralization of the acid 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, -d. h.

Aralkyl hydrocarbon radical with 6 to 25 carbons tert-dodecyl-NH-CHjjCHOHCHaOH, is in a (i

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 ⁰ C is kept.

C ₁₆ alkyl fractions of coconut amine, cyclohexyl, the mixture is at 60 to 70 ⁰ C for a few hours

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

Hexylbenzyl, decylbenzyl and octadecylbenzyl. R '"rungsreäktion completed. It forms

is either a hydroxyethyl or a hydroxy 30 N- (2,3-dihydroxypropyO-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.

oxyd 'are obtained. Another way for the profit- The reaction mass is with kerosene too

tion of this class of amines, where R '"is 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 add amine salts in the neutralization stage

By using the new. used dissolved in kerosene or methanol

Compounds will be the properties of distillate, said salt directly as free loading u

fuels significantly improved. . 45 possible solution of e.g. 80 percent by weight in

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

Since the process for the production of the acidic alkyl-alkanolamine salts of alkyl ester phosphates, the phosphate is added to a mixture of the mono- and dihydrodem gasoline, of decisive, it is of far importance for the practice as long as the The amount added is sufficient to allow this mixture to be used in the production of the amine salts of gasoline with regard to the undesirable properties. To improve throttling of the resulting alkanolamine salt mixture. When adding to the gasoline can then be used directly as a gasoline additive, amounts of salt from about 0.0003 to about 0.02% are required - preferred. The gasoline mixtures can then be obtained by separating, in addition to the alkanolamine phosphate salts, all those initially containing the monohydrogen phosphate from the di-additives that are incorporated into modern gasoline and then isolating them. Examples of such additives are antitic acid phosphates with a certain alkanol knocking agent, antioxidants, dyes and metal amine to react. The separation of the monohydrate deactivators, which do not adversely affect the behavior of the salts added according to the invention from the salts added according to the invention, is carried out in a manner known per se. So the addition of the invention in gasoline can compatible for example, _x the di-ox'o-tridecylhydrogenphosphat are. For the use of the salts as an agent against undesired throttling in gasoline, separated from the mono-oxo-tridecyl hydrogen phosphate, it is preferred and obtained, as in the USA patent, the salts in a solvent such as methanol, 65 documents 2,818,421 and 2,854,468. The kerosene or xylene, in sufficient concentration of di-oxo-tridecyl hydrogen phosphate, is dissolved in concentrations in order to produce 50 to 80 weight percent salt solutions with N- (2,3-dihydroxypropyl) -tert-dodecylamine. 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, whereby corresponding salts are produced as additives according to the invention.

Example II

Table I.
Dihydroxyalkyl amine salt components

H Alkanolamine Acid
Phosphates *) (A) RR ']
R. H -J-CH ₁ -CH (OH) CH ₁ 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. -Ci ₈ - to Tridecyl n-butyl C ₂₄ AkVI fraction Tridecyl H Phenyl Tridecyl H n-butyl Isooctyl **) tert-dodecyl Hexadecyl tert-dodecyl

»5

Table I still

Alkanolamine Acid
Phosphates *) R " (B) R "N (R '"),
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 Cj ₂ - to C _ie -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

30th

35

Gasoline samples containing alkanolamine phosphate salts according to the invention are prepared 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 carried out with regard to carburetor icing and contamination. The samples are thereby prepared that small amounts of the respective alkanolamine phosphate salts are added to the gasoline; for details see Table II, IH and IV.

The gasoline used in the experiments is a commercial product and shows the following properties:

Reid vapor pressure .. 0.91 kg / cm ⁸

ASTM distillation (D86) ⁰ C

Initial boiling point 24

50% ■; · ... 90

90% 170

End boiling point 208

The following is a brief description of the test conditions and the devices used to determine the samples.

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, ⁰ / ,, ....

Motor load in PS ...........

Motor speed, rpm

Idle speed,
RPM

Fuel temperature
to the carburetor in ⁰ C.

Carburetor type

throttle

3 to 5 1 to 2 98 to 100 98 to 100

10 15

1500 at ho-1500

here prisoner

dizzy

speed

350
10 to 13

Mixing tube

10 to 13

55

(a) Throttle valve carburetor

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

**) The information Tridecyl and IsooctyJ in this table refer to the groups in Oxo-tridecyl and Oxo-octyl alcohols are present.

The operating time of the engine is varied under the specified conditions; which are stifling Elapsed time is taken as a measure of the fuel caused by carburetor icing Cause or prevent stalling. All attempts are recorded after previously the gasifier flap is treated with methanol at a temperature of 5 ° C for a period of 0.5 minutes has been. The operating time used in each case for the engine depends on the tendency of the fuel to Ice formation. The operating times for an engine

409623/180

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 Anti-ice behavior rated. .

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 of tests in which the gasoline alkanolamine salts according to of the invention in amounts effective against the appearance of stalling are in the following Table II summarized.

The unique property of the invention Additives when using engines

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 known that additives in one of the carburetors

* 5 types are effective, not necessarily at 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) RR'N - CH, - CH (OH) CH ₁ OH TJ H Ώ ' Sour Weight percent
of the additive
in fuel Throttle valves
carburetor
Stall time * . Mixing tube carburetor
Motor top speed
speed R.
• \ K. Phosphate*) in minutes tert-dodecyl Tridecyl > 3.00 RPM 0.002 '3.00 H 0.004 1250 0.008 1400 H 2,4-dimethyl 0.012 3.00 1450 Cyclohexyl phenyl Tridecyl > 3.00 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 n-butyl kyl fraction 0.016 1300 Phenyl Tridecyl n-butyl Tridecyl 0.006 1000 H 0.003 0.004 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)
rm R "Nm""L R. ηt'f - - - - Treat Weight percent
of the additive Throttle valves
carburetor Mixing tube carburetor
Motor top speed n-dodecyl. R. Phosphate*) in fuel Stall time speed CH ₂ CH ₂ OH ^;; . Tridecyl in minutes . ■■■■: .- ■. ■■■ RPM 0.001 1350 Phenyl 0.002 '".- ■ 2.25 1475 n-octadecyi CH ₂ CH ₂ OH Tridecyl 0.003. 3.00 CH ₂ CH ₂ OH Tridecyl 0.004 1500 Tall alkyl 0.006 1150 n-octadecylhexyl CH ₂ CH ₂ OH Tridecyl 0.004 1.00 Cyclohexyl CH ₂ CH ₂ OH Tridecyl 0.016 2.50 CH ₂ CH ₂ OH Tridecyl 0.008 1350 0.006 2.25 ■ ■. n-dodecylbenzyl 0.002 1375 CH ₂ CH ₂ OH Tridecyl 0.004 1475 0.004 1475 n-dodecyl 0.004 1300 Coconut alkyl CH ₂ CH ₂ OH Isodecyl 0.012 1430 CH ₂ CH ₂ OH Isooctyl 0.016 1500 Coconut alkyl 0.006 1500 CH ₂ CH ₂ OH mixed Q ₂ - 0.002 1375 up to Q ₆ -Al- 0.004 1450 Coconut alkyl kyl fraction 0.004 1250 CH ₂ CH ₂ OH Di- (2-ethyl- 0.012 1450 Coconut alkyl hexyl) Coconut alkyl CH ₂ CH ₂ OH Hexadecyl 0.004 1300 Cyclohexyl CH ₂ CH ₂ OH Tridecyl 0.008 1475 CH ₂ CH (CH ₃ ) OH Tridecyl 0.002 1400 0.004 3.00 1500 n-dodecyl 0.001 1.25 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 III
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 0.004 speed Solution in solvent) Isooctyl 0.008 age
RPM 0.004 900 Amine Isooctyl 0.008 900 2-ethylhexyl 0.004. 1150 C ₈ - to C ₁₈ - 0.008 625 2-ethylhexyl Alkyls from 0.004 950 Coconut oil 0.016 1150 N-tall-1,3-di- Di-2-ethyl 0.004 1100 aminopropane hexyl 0.016 750 C ₁ J- to Q ₅ - 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 specified.

Comparative tests are made under the appropriate test conditions to demonstrate the effect of various unsubstituted amine phosphate salts on the engine stall phenomenon. The results are summarized in Table IH below.
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 becomes stronger as the amount of the additive increases.

In addition, the alkanolamine salts according to the invention show a superior effect over the unsubstituted amine salts in tests with conventional throttle valve carburetors. For example, when using a commercially available gasoline having an average boiling point of 110 ⁰ C as the base fuel is achieved Abwürgzeit of 3 minutes in the throttle carburetor when 0.008 weight percent (80% active ingredients) of the acidic Tridecylphosphats be used the 2-Äthylhexylaminsalzes. However, only 0.0016 percent by weight (80% active ingredients) of the n-dodecyl diethanol amine salt of acid tridecyl phosphate is required to

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 experiment can also be carried out on a mixed tube carburetor be applied.

Carburetor cleaning effect '

The carburetor cleaning effect of the invention Alkanolamine phosphate salts can be determined on a Lausen test engine which is equipped with a Tillotsen carburetor is provided which has removable leaflets around the throttle valve. While The experiment gets some of the exhaust from a second single cylinder engine running at constant speed is operated by 2500 rpm, introduced into the to be tested ao the carburetor. The test engine is running during a period of 2 hours, 1 minute each time with the throttle valve open and under dynamometer load and then operated for 2 minutes at idle at 1100 ± 100 rpm. After the end of the experiment the leaflets are removed and graded on a scale from 1 to 10, with the number 10 being a a shiny, shimmering appearance and the number 0 mean very heavy black precipitation. the The basic fuel for this test is the same as for the previous anti-ice tests.

: The comparative consideration of the leaflets from a carburetor after the engine with the basic gasoline had been operated with leaflets from a carburetor after running the engine with one Gasoline containing the additives of the invention shows the effective cleaning power of the additives of the invention Additives. The results of this comparative consideration are as follows Table IV given. '

From this table it can be seen that high cleaning effects in the gasifier with very small amounts of the alkanolamine phosphate salts according to Invention can be achieved in 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-Ci ₈ - 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) RR ⁷ N - CH, - 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

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

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

Claims (3)

Patent claims: 1. Salts of acidic primary alkyl orthophosphates in which the esterifying alkyl radicals have 8 to 16 carbon atoms contain, with an equimolar amount of alkanolamines of the general formulas (A) RR'N - CH ₂ CH (OH) CH ₂ OH or (B) R "N (R '") ₂ in which R and R 'denote hydrogen, alkyl, cycloalkyl, phenyl or alkylphenyl with the proviso that R and R 'together have 8 to 24 carbon atoms, R "is an alkyl, cycloalkyl, phenyl or aralkyl each having 6 to 25 carbon atoms and R '"is a hydroxyethyl or hydroxypropyl radical mean, where, when R "is an alkyl radical, those alkyl groups are excluded which the general formula CH- in which R _{1 is} a straight-chain alkyl radical having 1 to 3 carbon atoms and R _{2 is} a straight-chain alkyl radical having 5 to 22 carbon atoms. 2. Process for the preparation of compounds according to claim 1, characterized in that at least one acidic primary alkyl orthophosphate, in which the first alkyl groups Containing 8 to 16 carbon atoms, with an equimolar amount of an alkanolamine of the general formula or RR'N - CH ₂ - CH (OH) CH ₂ OH
R "-N (R '") ₂ wherein the radicals R, R ', R "and R'" have the meaning given in claim 1, in per se implemented in a known manner. 3. Use of compounds according to claim 1 as an additive for fuel mixture on the Based on hydrocarbon distillates that are liquid under normal conditions. in turn causes the condensation of the moisture entering the carburetor with the air, their Water particles on the edge of the throttle valve and on. the carburetor air supply freeze up. The ice formation at the edge of the carburetor flap reduces the air flow to the engine, which is thus throttled or is stalled. In addition, the formation of ice on the air inlets or venturi pipes leads to stalling of the engine as a result of an excessively rich mixture. ίο Such ice formation also takes place in the mixing tube carburetors, which are mainly used in motor vehicles of foreign manufacture. In such a mixing tube gasifier, air and fuel are mixed, flow out in a balanced amount and are then gasified. The ice forms first at the inlet of the air correction nozzle of the mixing tube, which can lead to the engine throttling or stalling.
Frequent throttling of the engine can also be traced back to operating conditions, which are caused by high traffic loads when stopping and starting up, when the engine is frequently operated in idle. The stalling of the engine in such traffic behavior is mainly due to the accumulation of foreign materials on the walls of the throttle valve body, which is located below the closed throttle valve. Foreign matter can enter the carburetor at idle speed because the air filter is relatively ineffective at these speeds. Most of the debris or foreign matter that reaches the carburetor at idle speeds is blown out of the engine through the crankcase ventilation. However, the contaminants remain trapped under the hood when the car is stopped and can easily enter the carburetor when the engine is idling. Other sources of pollution include the exhaust gases from the front cars, as well as the usual smoke and dust present in the air as a result of traffic conditions that require engines to operate under heavy loads. Although it is well known that this source of error can be eliminated by increasing the engine idling speed, this is disadvantageous in that it increases fuel consumption. The invention relates to salts of acidic primary alkyl orthophosphates, in which the esterifying alkyl radicals contain 8 to 16 carbon atoms, with an equimolar amount of alkanolamines of the general formulas