DE1720446B2 - Amine phosphate ester salts and their use as detergent additives for fuels - Google Patents

Description

in which χ an average number from 1 to 2, y an integer from 1 to 5, ζ at least 1 and up to 90% of the titratable amine nitrogen corresponding amount, U an alkylene group with 2 to 6 carbon atoms, R a hydrocarbon radical , which is essentially free of aromatic unsaturation, with a molecular weight of 400 to 5000, A is an alkyl group having 8 to 24 carbon atoms and B is hydrogen or an alkyl group having 8 to 24 carbon atoms.

2. A compound according to claim 1, characterized in that χ a number from 1 to IA y a number from 1 to 4, ζ a number between 1 and (y— 1), R a branched-chain aliphatic radical with a molecular weight of 400 to 3000 , A is an alkyl group having 10 to 20 carbon atoms and B is hydrogen or an alkyl group having 10 to 20 carbon atoms.

3. Compounds according to claims 1 and 2, characterized in that B is a mixture of Is hydrogen and alkyl

4. Liquid fuel based on hydrocarbons, especially gasoline, thereby characterized in that it contains a compound according to claim 1

40

The requirements that are made of fuels go far beyond the fact that these are only one Represent a source of power. The fuel oils are mixed with additives to provide protection against corrosion during storage and handling and that transport is achieved; the additives also serve to prevent the secretion of oil sludge in internal combustion engines, especially in the carburetor and in other places that are connected to the fuel oil Come into contact. Additives that serve this latter purpose are called detergent additives designated

Additives are also added to the fuel to prevent the gasoline from icing up during the winter months. The ice forms through the Cooling effect during the evaporation of the fuel and the condensation of those contained in the atmosphere Moisture, which stalls the engine, especially when idling

The additives that are in the fuels not only have to perform the task set for them; they are also not allowed to The fuel nor the engine adversely affect it, they must have more in the fuel existing additives be compatible and they in turn must not add additional problems such. B. that Problem of water tolerance.

It is known that hydrocarbon-substituted alkylene polyamines are effective detergent additives for Fuels, such as disel oils and gasoline, are. aside from that are amine salts of alkyl phosphoric acid esters, in soft the hydrocarbon monoamine contains 6 to 24 carbon atoms, as a fuel additive, which counteract the formation of ice and provide corrosion protection, known (see US Pat. No. 32 28 758, 2863 742).

Furthermore, from US-PS 30 35 905 the use of a salt of a hydrocarbon diester Phosphoric acid with 6 to 22 carbon atoms in the hydrocarbon groups and one aliphatic Hydrocarbyl diamines having no ment as a hydrocarbyl substituent of 6 to 18 carbon atoms known on nitrogen as a multipurpose additive for fuels for internal combustion engines, which inter alia. it is also intended to prevent the formation of deposits it can be seen whether and what influence a hydrocarbon substance exerts on nitrogen can at best conclude that salts of diamines, such as 1,2-propylenediamine or N-hexyi-ethylenediamine, those who have no or only a small alkyl substituent on the nitrogen see good detergent additives meant to be. However, it will be shown below that the hydrocarbon substituent on Nitrogen to act as a detergent additive is quite important, even a relatively larger one proposed in this patent specification Alkyl substituent in an ammonium phosphate ester salt does not prevent sludge deposits causes

It has now been found that the amine phosphate ester salts according to the invention, which are formed by long-chain hydrocarbon radicals substituted alkylene polyamines containing at least two amino nitrogen atoms and are partially neutralized with alkyl phosphate esters, represent, represent not only excellent detergent additives, but also effective at the same time Anti-icing agents and anti-corrosion agents are. The alkylene polyamines range from 2 to 6 Nitrogen atoms with alkylene groups with 2 to 6 carbon atoms, preferably 2 to 3 carbon atoms, and 1 to 2 long chain hydrocarbon substituents. The hydrocarbon substituents generally contain 30 to 300 carbon atoms, preferably 30 to 150 carbon atoms. In which Phosphoric acid ester can be a mono- or be a diester or a mixture of these two esters, the alkyl groups with 8 to 24 Carbon atoms, preferably 8 to 20 carbon atoms.

The compounds according to the invention are relatively high molecular weight branched chain ones alkylene polyamines with a molecular weight of 450 and hydrocarbon-substituted on the nitrogen atom up to 5000, even better 450 to 3500, some of which are esterified with a mono- or dialkylphosphoric acid ester are; the alkylene polyamine has 2 to 6 nitrogen atoms, preferably 2 to 5 nitrogen atoms. It is preferably the hydrocarbon-substituted ones Alkylene polyamines to known polyisobutylene-alkylene polyamines with 1 to 2 polyisobutylene groups per alkylene polyamine and 2 to 5 nitrogen atoms and

an average molecular weight between 450 and 1500.

The compounds according to the invention correspond to the formula

R, H, _ _{x + l} i; (NU), NH] · ζ

HO-P-OA

IF

Formula have the symbols following

In this
Meaning:

χ a number from 1 to 2 (often on average between 1 and 2%
an integer from 1 to 5,

at least 1 and up to an amount which is 90% of the; titrable amine strength *),
Alkylene having 3 to 6 carbon atoms, preferably 2 to 3 carbon atoms,

R is a hydrocarbon radical that is essentially free of is aromatic unsaturation and is a molecular weight has from 400 to 5000,

A alkyl group with 8 to 24 carbon atoms,

B hydrogen or an Aikyign ^ ipe with S to 24 Carbon atoms, which can be the same or a different group from A.

·) The following i meode was used:
A sample of the product of about 0 g is dissolved in 100 ml of a solution of toluene to isopropanol to water in a volume ratio of 50: 45: 5 and titrated metrically with 0.1 N hydrochloric acid, cod using a Calomel electrode against a Gto electrode (Pt) in an automatic taring device.

Particularly useful compounds correspond to the formula

HO — P-OA '

IF'

Alkylene polyamine, either directly or in a suitable solvent, e.g. Hydrocarbon. A liquid hydrocarbon is preferably used as the fuel and provided first a fuel concentrate. The reaction can be carried out at room temperature and does not require any special reaction conditions or special precautionary measures.

The hydrocarbon-substituted alkylene polyamines which are used are known and correspond the formula

In this formula, the symbols have the following meanings:

χ 'is a number from 1 to 2, preferably from 1 to 1.6,

y 'is a number from 1 to 5, preferably 1 to 4,

ζ 'is a number in the range from 1 to /, preferably im

Range from 1 to (/ - 1),

R 'is a branched chain aliphatic radical with a molecular weight of 400 to 3000, preferably 450 to 1500,

A 'is an alkyl group with 10 to 20 carbon atoms,
B 'is an alkyl group having 10 to 20 carbon atoms

or hydrogen,
U 'is an alkylene group with 2 to 3 carbon atoms.

A mixture of mono- and diester is preferably used, i.e. half of B 'consists of Hydrogen and half from alkyl.

The phosphate salt is made by adding the equivalent weight of the hydrocarbon-substituted Alkylenepolyamine by titration with hydrochloric acid (in the manner described above) determined and then the necessary amount of phosphoric acid ester to the hydrocarbon-substituted is in which the symbols have the meaning already given.

Examples of hydrocarbon substituents are aliphatic and alicyclic substituents which are im are essentially free of aromatic unsaturation.

The hydrocarbon residues can be from Oicfiupöiymeren with 2 to 6 carbon atoms (in the case of ethylene this is generally with an olefin with at least 3 carbon atoms mixed polyserized) or may be from naturally occurring Relatively high molecular weight products, e.g. B. naphthenic bright stock or neutral oils, be derived. Examples of hydrocarbon substituents are polyisobutylene, polypropylene, poly-4-methylpentene-1.

Examples of alkylene polyamines are

Ethylenediamine, diethylenetriamine,
Tetraethylene pentamine, 1,3-propylenediamine,
1,2-propylenediamine, tetramethylenediamine,
Dipropylenetriamine.

The phosphoric acid esters which are useful for the purposes of the invention are known and correspond the formula

O
HO-P-OA

IF

in which the symbols have the meaning already given.
Examples of suitable phosphate esters are:

Monodecyl, didecyl, didodecyl,
Ditridecyl, monotridecyl, octyldecyl,
Decyl dodecyl phosphate

As already said above, the diester alkyl groups identical or different seia Mixtures of mono- and diesters are preferably used, the molar ratio of monoester to diester being in the range of about 1: 0.8-1.2

The following examples serve to further illustrate the invention.

example 1
Production of the polyalkylene polyamine

In a flask was placed 1580 g of a 75% active solution of polyisobutenyl chloride (molecular weight about 1100, 1.2 moles), 494 g (43 moles) diethylenetriamine and 300 g of butyl alcohol. Under a nitrogen

atmosphere the mixture was at 135 ° C for 5 hours heated, the solvent distilled over. At the At the end of this time, the reaction mixture was taken up in 800 ml of toluene; the mixture was raised to 75 ° C heated and treated with 105 g of 95% alcohol and 400 g of water. The mixture was cooled, the Separated phases and discarded the aqueous phase. The washing process was repeated three times organic phase was distilled off by slowly heating the solution to 123 ° C, water and Toluene was withdrawn overhead. The residue was 1801 g. The active part (determined by Nitrogen analysis) was 55.25 percent by weight titration with 0.103 n-hydrochloric acid (below the Assumption that only 2 nitrogen atoms can be titrated) showed that the solution was 49.7% active.

Salt formation;

20th

Part of this solution is one sufficient amount of a mixture of mono- and ditridecyl phosphate in the molar ratio 1 :)., so that a mixture of the polyisobutenyl diethylenetriamine with the Phcsphsissicm in the ratio 1: 1 resulted.

A number of compounds were made in a manner similar to that in the tables below is reported.

The compounds of this invention can be used in a wide variety of liquid hydrocarbons whenever the presence of small amounts of water causes corrosion problems The compounds of this invention find particular use in fuels in which they not only result in corrosion protection, but also as detergent additives and prevent ice formation Means work. The fuels include diesel oils, gasoline and kerosene.

Depending on the intended use, amounts as low as 2½ parts per million (TPM) phosphate salt can be used to effectively prevent corrosion; however, generally at least about 5 but not more than about 50 parts per million will be used to achieve corrosion prevention. At least 15 parts per million and generally no more than 0.1 weight percent are used to prevent sludge and ice formation. Excellent results are most often obtained with additive concentrations of 100 to 5000 TPM.

The additives according to the invention are special Can be used for volatile fuels and fuels that have vapor pressures according to Reid Ober about 9. Included they are generally winter-type petrol used in northern areas where the Reid vapor pressures of the propellants are between approximately 9 and 13.5.

The additives according to the invention are compatible with other fuel additives. Examples of such additional additives are anti-knock agents, e.g. tetramethyl lead or tetraethyl lead, Lead detergents such as alkyl and aryl halides, additional Corrosion inhibitors, deposit modifiers, oxidation inhibitors and metal deactivators, Carburetor detergents.

A non-volatile j light lubricating oil, such as petroleum spray oil, is also a suitable additive for fuels in which the additives of the invention be used; they are preferably used together with these. It is believed that these Oils act as carriers for the active compounds according to the invention and remove deposits support as well as prevent the redeposition of the same. They come in amounts from 0.05 to 0.5 Percentage by volume based on the finished gasoline mixture

The effectiveness of the compounds according to the invention as corrosion inhibitors was as follows determined The two compounds selected as examples, i. H. those of Example 1 and a Compound with 2 moles of mixed phosphate esters per mole of polyisobutenyl diethylenetriamine were in a - as far as corrosion inhibition is concerned - particularly difficult fuel tested: a gasoline with a unleaded octane number of around 90 with a high content of both aromatics and reformates The test was used ii * db ASTM D 665-60 made using synthetic & eewater and the additive was used at a concentration of 30 TPM. The assessment was based on a comparison table of 1 ins 7, with 7 more complete Rusting and 1 corresponded to no rust formation. While the base fuels have a rating of 7 the two additives resulted in & h. the one with one mole and the other with two moles of mixed phosphate esters each have a rating of 1. (There was a trace of rust with the additive with only one mole of mixed phosphate ester)

About the usability of the compounds according to the invention as a means of preventing icing of engines was shown a number of the compounds in a laboratory engine test like is checked as follows:

The carburetor used was the one developed for the 1965 Plymouth 3687 cm ³ engine, which was operated on a Plyroouth head 3769 cm ³ engine. The carburetor is thermally isolated from the engine and is kept in a heated state during the tests by a controlled heating element. As soon as an equilibrium temperature has been established in the Vsrgaser the engine is started and accelerated to 2400 rpm - no load - and thus kept in operation for 30 seconds. The engine speed is then reduced to idle (525-550rpm) for 15 seconds. As soon as the engine fails or after 15 seconds, it accelerates again to 2400 revolutions per minute - no load. This cycle is repeated 14 times; during this time the air supplied and the carburetor gradually heat up. The air supplied initially has a temperature of 4.44 ° C and a relative humidity of 100%; the temperature rises gradually to 21.1 ° C during the determination.

Examples 2 and 3

The table below shows the effect of the additives according to the invention against ice formation on reducing the frequency of engine outages with difficult winter fuels The additives were present in amounts of 30 TPM.

Table I.

additive Moles of phosphate average Defin Amine ¹ ) ester ² ) / actual number of mungen per mole of Appearance Amines

7.4
6.9
6.2

8.2

7.5
7.3
8.8

3
3
3
3
Il

) H l'nlyisohutynyldiilhyltriamine (f'olyisobulenyl mil about 570 molecular weight;% N, 6.25).
Ml l'olyisohulenyltriethylenetetramine (l'cilyisohutenyl with about ⁽ > 5 () molecular weight;% N, 5.11).
") Molar ratio I: I.

In order to show the excellent effect of the compounds according to the invention in preventing sludge deposition, the following experiment was carried out: A Plymouth L-head engine and a clean glass intake port were used and the engine was initially operated for one hour with a fuel without additives, the fuel mixture being less than twice Compression was fed to the vas inlet and the air-fuel mixture was air-rich. The conditions were as follows: jacket temperature 7ΓC; oil temperature about 54 ⁰ C; Engine speed 500 RPM accelerated to 2000 RPM five times in succession every 7 1/2 minutes; no burden. The engine was then run on fuel containing an additive for four hours, the fuel mixture being fed to the carburetor without double compression and the air / fuel ratio being normal. A comparison of the intake manifold at the end of the first one hour period and at the end of the second period during which the additive-containing fuel was used enables the percentage of deposits removed by the additive-containing fuel to be determined.

This experiment is generally carried out at least four times; the results are as averages given from all experiments.

The samples used were the parent amine and the basic amine, some of which were included a mixture of mono- and di (tridecy!) phosphate im Molar ratio! : 1 was neutralized. The results given show the percentage improvement in the Phosphate salt over the parent amine, i.e. the difference in the percentage removal of the deposits. The results are summarized in the following table:

Table II

Additive Moles of phosphate Percentage Defin Amine ¹ ) ester per mole improvement mungen of the amine compared to the Additives ¹ ) Parent amine

23
22nd

Further attempts to prevent deposits were carried out as follows: A single cylinder CRF engine, which was equipped with an intake manifold, was under the following operating conditions 3 inserted:

Jacket temperature, ° C 100 oil temperature, ⁰ C 66-82 Temperature of the incoming Air, ⁰ C 35 Determination of the ignition point "BTC 15th Inlet manifold vacuum, mm Hg 381 Fuel / air ratio 0.07 Running time, hours 12th Speed, r.p.m. 1800

The evaluation was based on the deposits forming on the inlet valve. At the end of the experiment, the oil and grease were carefully removed from the valve stem. Burn deposits were removed with a wire brush and the valve was weighed. The underside of the valve was then washed with hexane until the hexane cleared, and then the valve was placed in an oven at 9? dried up to 116 ° C. After cooling, the valve was weighed, all debris was removed, and the weight of the valve was determined. Three samples were prepared using a commercially available gasoline and an addition of 100 TPM of the agents to be tested and 400 TPM of a neutral oil refined with the aid of a solvent with a density of 0.922 g / cm ³ and a viscosity of 363.6 cSt.

B e i s ρ i eIe 4 and 5

The following compounds were used as amines in the additives:

Compound IV: (comparison)

a well-known NA! ky! propane - !, 3 diarnin,
Alkyl group is derived from tallow acids;

whose

) see table I.

Connection V:

a substituted by a polyisobutenyl group Tetraethylene pentamine, the polyisobutenyl group of which is a (determined by viscosity measurement) has an average molecular weight of about 1,000;

Compound VI:

an ethylenediamine substituted by a polyisobutenyl group, the polyisobutenyl group thereof Average molecular weight (determined by viscosity measurement) of about 1400 having

The above three compounds were each based on the base number of the amine and the acid number the acid, 90% neutralized with a mixture of Mono- and ditridecyl phosphate in a molar ratio of 1: 1. The results obtained with these additives are in the following table III compiled:

Table HI

Additive from compound Weight of the deposit
on the valve, mg unwashed washed IV ! 19 90 V 91 56 VI 53 29 Fuel tank base (un
leaded gasoline) 90

It can be seen from the results in Table IH that the amine phosphate ester salt used as a comparison substance of Compound IV at 100 TPM to prevent valve scale

however, the amine phosphate ester salts according to the invention are obvious the higher molecular weight compounds V and VI are effective in reducing the amount of deposits.

Examples 6 to 8

There were four more amine phosphate ester salts in the same manner as the amine phosphate ester salts of the in the example above in a single cylinder CFR engine under the following operating conditions:

Jacket temperature, ° C 100

oil temperature, 66-82 ° C

Temperature of the incoming

Air, ⁰ C 35

Determination of the ignition point,

⁰ BTC 15

Inlet manifold vacuum, mm Hg 381 Fuel / air ratio 0.07 Running time, hours 12 Speed, r.p.m. 1800

The tests were carried out in commercial gasoline with an addition of 100 TPM of the additive to be tested and with the addition of 400 TPM of a solvent-refined neutral oil with a density of 0.922 g / cm- 'and a viscosity of 363.6 cSt carried out

The following compounds were used as amines in the additives:

Compound VII:

an ethylenediamine substituted by a polyisobutenyl group, the polyisobutenyl group thereof Average molecular weight (determined by viscosity measurement) of about 560 having;

Compound VIII: (comparison)

a well-known N-alkylpropane-l ^ -diamine, its Alkyl group is derived from tallow acids;

ι Connection IX:

a tetraethylene pentamine substituted by a polyisobutenyl group, its polyisobutenyl group an average molecular weight (determined by viscosity measurement) of about

has in 1000;

Connection X:

an ethylenediamine substituted by a polyisobutenyl group, the polyisobutenyl group thereof ΙΊ (determined by viscosity measurement) average Has molecular weight of about 640.

t-flX. TlUl VWlJtUIIbIlUbIl T Ul UlIlUUI IgCIl W Ul UCII JC W Cl 13,

.Mi based on the base number of the amine and the acid number the acid, 90% neutralized with a mixture of mono- and ditridecyl phosphate in a molar ratio of 1: 1. The results obtained with these additives are summarized in Table IV below:

Table IV

Additive
Link:

Weight of the deposit
on the valve, mg

unwashed

washed

45 33 446 411 24 19th 73 37

VII
VIII

From the results in Table IV it can be seen that the amine phosphate ester salt used as the comparative substance of Compound VIII at 100 TPM to prevent valve deposits In contrast, the amine phosphate ester salts of the compounds of the present invention are not effective Higher molecular weight VH, IX and X are very effective in reducing deposits.

It is clear from the above results that the compounds according to the invention give fuels a wide range of improved properties. The excellent detergent effect Not only is it preserved, it is surprisingly improved; but also the Corrosion protection, in particular the rust protection and the anti-ice effect, are also reinforced Compounds with other additives that are usually present in fuels, compatible.

Claims (1)

Patent claims:
1. Amine phosphate ester salts of the formula R, H _y _ _{x + 1} ((NU) _y NH) · ζ HO-P-OA IF to