DE2401930A1 - POLYALKYLENE GLYCOL POLYAMINES AND FUELS CONTAINING THESE - Google Patents

Description

PATENT LAWYERS

DR.-ING. RICHARD GLAWE - DIPL-ING. KLAUS DELFS MUNICH HAMBURG

DlPL-PHYS. DR. WALTER MOLL MUNICH

8 MONKS 26 PO Box 37 UEBHERRSTR. 20th TEL. (0811) 22 65 48 TELEX 52 25 05 ipez

2 HAMBURG 52 WAITZSTR. 12 TEL. (0411) 89 22 55 TELEX 21 29 21 spec

YOUR SIGN YOUR MESSAGE FROM OUR SIGN A 61 REGARDS:

MUNICH

BP gasoline and petroleum shares Hamburg

Polyalkylene glycol polyamines
and fuels containing them

This invention relates to polyalkylene glycol polyamines of the general formula

H ^ 0-CH ₂ -CHR ₁

E,,

in the

, R, and R. Hydrogen atoms and / or polyalkylene glycol

5O983Ö709 "23

remnants of the general formula

H -T 0-CH ₂ -CHR ₁

R _{1 is} a hydrogen atom and / or a methyl group and Rt- is a divalent, saturated, aliphatic hydrocarbon radical with 2-6 carbon atoms and χ has a value of 5-50 and ζ has a value of 1-4, obtainable either by reaction of a polyalkylene glycol consisting of a polypropylene glycol and / or a polyethylene glycol and / or a polypropylene / ethylene glycol of the general formula

H- ^ O-CH ₂ -CHR ₁ 4- OH,

in which R ₁ and χ have the meaning given above, with hydrogen chloride in a molar ratio of about 1: 1 and then with a polyamine of the general formula

H, "ζ

in which R ₁₅ and ζ have the meaning given above, or duroh reaction of propylene oxide or ethylene oxide or mixtures thereof with the polyamine, as well as fuels containing these polyalkylene glycol polyamines.

509830/0923

Prevent the polyalkylene glycol polyamines of the invention as additives in fuels for gasoline engines, the pollution of critical parts of the engine, in particular the inlet paths including the carburetor and the inlet valves.

From DOS 2 229 945 are polybutenylalkylenepolyamino alcohols the general formula

known, in the R. a polybutenyl radical with a molecular weight is from about 400-50,000. These compounds can be used as dispersants for mineral lubricating oil formulations will. From DOS 2 244 513 are polyamine-modified te polyalkylene oxides known that are obtained by reacting polychlorinated Polyalkylene oxides of the general formula

C CH ₂ OH (CH ₂ Cl) -O ^ P3H (CH ₂ Cl) -CH (CH ₂ Cl) -O

can be obtained with appropriate amines. These compounds can be used as flocculants. The known Compounds thus differ both in chemical terms and in terms of their areas of application from Compounds of the invention.

S0983070923

■ Due to the technical requirements and the legal regulations for keeping the air clean, the engine manufacturers are forced to make design changes to motor vehicle engines. For example, to reduce air pollution from hydrocarbons which have not been or are incompletely burned, the crankcase ventilation is not fed into the open atmosphere, but into the intake system upstream of the carburetor. However, this measure causes contamination of the intake system, which contamination occurs in particular in the carburetor and on the intake valves. These deposits form a constant problem in ensuring the proper operation of internal combustion engines. They cause malfunctions that not only have a negative effect on fuel consumption and the performance of the engine, but are also the cause of increased emissions of unburned and partially burned hydrocarbons. They can thus indirectly contribute significantly to air pollution. To VermeIdUiL ₀ ¹ these disadvantages, sets the fuel small amounts of certain Verbindunger to having detergent properties.

A major disadvantage of the known additives of this type is that, although certain properties of the fuels improved, while others can be negatively influenced. Such additives must, however, be expected that on the one hand they are able to remove formed residues again. On the other hand, in the case of thermal

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mixed loads do not form any residues ", ie do not make their own contribution to pollution. However, the last-mentioned disadvantage in particular is with carburetor detergents based on fatty acid amide or I-fatty acid imidazoline available. Such additives have good properties with regard to keeping the gasifier clean but completely ineffective for keeping the valves clean j in part they even contribute to the increase in deposits at.

Detergents, in particular emulsifiers, also pose a problem in what is known as the water release capacity of the Fuels, since often not only the undesired residues are kept in a dispersed state, but also the settling of water is also prevented. This problem of reduced water separation is a serious one This is important because fuels can often come into contact with water during transport. For this reason, the Storage tanks are normally provided with appropriate water separation devices in order to keep them in the water during transport To be able to remove water that has got into the fuel. At Schleohtem These devices are not sufficient to separate the water from the fuel, and there is a possibility ^ that fuels are delivered that as a result of their water ■ water content in engines can lead to malfunctions.

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For the perfect operation of carburettor engines you still need in the cold and humid season Additives that prevent the carburetor from icing up. For this purpose, in addition to the detergents mentioned, are generally used still other additives, 25.B. Isopropanol or dipropylene glycol j added, which act as solubilizers or freezing point depressants. It can also be surface-active Substances with bifunctional molecules are used, which are adsorbed on the inner surfaces of the carburetor and due to their hydrophobic properties a build-up of Prevent water or ice. Mixtures of such additives are also used.

The invention is directed to polyalkylene glycol polyamines of the type mentioned, which are used as additives in fuels very good cleanliness of the intake system of gasoline engines and also a good anti-icing behavior have without the aforementioned adverse effects occurring.

Preferred polyalkylene glycol polyamines of the invention are those whose polyalkylene glycol radicals have molecular weights in the Range from about 800-1,200. Polypropoxylated or polyethoxy / propoxylated are particularly advantageous Polyamines in which the number of propylene oxide units in the polyalkylene glycol residues is in the range of 5-20 or the 'the ethylene oxide units is in the range of 0-20.

509830 / ^ 0 * 23

Alkylenediamines can be used as polyfunctional aliphatic amines with preferably 2-6 carbon atoms in the hydrocarbon radical, e.g. ethylenediamine, propylenediamine or the like., or polyamines, e.g. diethylenetriamine, triethylenetetramine Or the like., Are used. However, polyamines with branched or cyclic hydrocarbon radicals can also be used saturated heterocyclic polyamines can be used.

By varying the ratio of the propylene oxide units to the ethylene oxide units in the polyalkylene glycol residues the compound of the invention can impart more or less pronounced anti-icing properties to the additives will. The increase in the proportion of ethylene oxide units generally leads to a gain this effect.

The additives containing the polyalkylene glycol polyamines of the invention can generally be added to the fuels Torrn of a concentrate are added, the solvent preferably being an aromatic hydrocarbon, e.g. toluene or xylene is used. The concentration at which the polyoxyalkylenepolyamines of the invention are in the fuel present is generally 0.001-0.5, preferably 0.001-0.1 #

The cleaning effect of the additives of the invention can by adding a high-boiling mineral oil cut, e.g.

S09830./O9-23

a refined paraffinic lubricating oil with a viscosity of 10 - 12 cSt / 210 ° F, in amounts of 0.01 - 0.2, preferably 0.01 - 0.1 G-ew .- $, based on the fuel, can still be increased. The improvement in the effect is probably due to the fact that relatively hard and solid residues are softened and can then be better detached and dispersed by the detergent.

In order to improve the anti-icing effect of the additives of the invention even further, they can also be used in a mixture with ethylated fatty alcohols. The ethoxylated alcohols are reaction products of straight-chain monohydric aliphatic alcohols of chain length Cq - C ₂₀ with ethylene oxide, the OH-G groups of the alcohols being etherified with a polyethylene glycol residue consisting of a maximum of 10 ethylene oxide units.

The ethoxylated petroleum alcohols which can be used to increase the anti-icing properties of the additives of the invention If necessary, the fuels are mixed in amounts of 0.001-0.1, preferably 0.001-0.05 Grew .- #.

Further preferred embodiments and advantages of the invention emerge from the following description and the Sub-claims.

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The invention is illustrated below using an exemplary embodiment for the preparation of the polyalkylene glycol polyamines Invention and explained in more detail on the basis of test results.

A. Preparation of a Monochloro Derivative of Polypropylene Glycol

100 parts by weight of a polypropylene glycol with an average molecular weight of about 1,000 are refluxed with 80 parts by weight of 37 percent hydrochloric acid for 20 hours. (Boiling range 40 - 6O ⁰ C) After cooling, the mixture with petroleum benzine in the ratio 2: diluted 1 and the solution washed with water until the chloride detection negative · is jarring is avoided to emulsion formation should be avoided. The petroleum benzine phase is evaporated to obtain the chlorine derivative. The chlorine derivative has a chlorine content of 3.3% by weight.

B. Preparation of a polypropylene glycol polyamine

62.5 parts by weight of the monochlorinated polypropylene glycol are refluxed with 11.0 parts by weight of potassium carbonate in 60.0 parts by weight of toluene. 6.2 parts by weight of diethylenetriamine are then added dropwise within 1.5-2 hours. Subsequently, the Eeaktionsansatζ is set still with 1.2 parts of potassium carbonate and held for 20 hours at 13O ⁰ C. After distilling off the toluene in Wasseretrahlvakuum the residue with petroleum benzine (boiling range 60 - 8O ⁰ C)

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taken up and wetted with the same solvent Filter given. The filtrate is evaporated to obtain the polypropylene glycol diethylenetriamine.

The product obtained has a nitrogen content of 0.45 percent by weight; the chlorine content is 0.

To test the effectiveness of the additive obtained in the manner described in more detail above, this was in a Amount of 0.01 percent by weight mixed with a petrol that had the following data »

d 15 ⁰ C ⁰ C. 0.767 - Start of boiling voi. i » 45 Transition to 100 ⁰ C ⁰ C 49 End of boiling mg / 100 ml 177 Evaporation residue 1 FIA analysis: Vol. Ji Aromatics VoI .Ji 39.5 Olefins g / l 25.5 Pb content (TML) 0.4 EOZ 99.8 MOZ 87.5. EOZ (100 ⁰ C) 95.5

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Examination of the cleaning effect on the intake system

A test engine was made with the additive fuel of the type Opel Kadett 11 SR (60 hp at 5,200 rpm) under operated under the following conditions:

Test duration:

Test program:

. "40 h

0.5 min idling at 950 rpm 1 min 3000 rpm and 15 hp

1 min 1300 rpm and 5.5 hp

2 min 1850 rpm and 8.5 hp

Test conditions: engine oil temperature:

Cooling water outlet temperature:

Intake air temperature: CO-G content at the start of the test:

~ 80 km / h)

35 km / h) 50- km / h)

94 ⁰ C max.

92 ⁰ C max. 100 ⁰ C max. *) 3.5 vol

*) To tighten the test conditions, the intake air preheated by means of heating coils.

The test fuel was also used under the same conditions tested without additives, mixtures of the test fuel and a high-boiling mineral oil cut as well as from the test fuel and two commercially available carburetor detergents, partly in combination with a high-boiling mineral oil cut. The high boiling point used

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509830/0923

de mineral oil cut consisted of a refined paraffinic base Lubricating oil with a viscosity of 12 cSt / 210 ° F.

The results obtained are summarized in the following table:

Table 1

Rating according to CRC Merit Eating (10 = clean)

fuel Carburetor Inlet
channels Inlet
valves Test fuel with 0.01 wt .- ^
Additive according to the invention and
0.05 wt. # Mineral oil cut 9.0 8.0 8.5 Test fuel with 0.01 wt .- #
Additive according to the invention without
Mineral oil cut 9.2 6.5 7.5 Test fuel without additive 6.5 ' 5.0 7.0 Test fuel with 0.05 wt .- ^ S
Mineral oil cut 6.1 6.5 8.5 Test fuel with 0.01 wt .- ^
Additive A (on fatty acid amide /
Fatty acid imidazoline base) 9.0 4.8 6.5 Test fuel with 0.01 wt .- ^
Additive A and 0.05 wt .- #
Mineral oil cut 8.6 7.5 8.5 Test fuel with 0.02 wt .- ^
Additive B (based on polyisobutenyl
polyamine base) 9.3 7.8 7.6

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509830/0923

The equivalence of these bench tests became practical ensured by comparative tests in vehicles of different types.

Testing of the water separation capacity

To assess the influence on the water release capacity 80 ml of fuel were mixed with 20 ml of distilled water. Waters in shaken in a standing cylinder and the cloudiness of the gasoline and water phase assessed after 5 and 15 minutes, respectively. The results obtained are summarized in the following table:

Table 2

fuel petrol
phase n.
5 min. 15 clear water
phase n.
5 min. 15 Between
layer n.
5 min. 15 Test fuel with
Additive according to the invention clear clear clear clear soharp
separation
of the phases Test fuel
without addition clear clear clear clear Il Test fuel
with additive A easy
cloudy clear clear clear 0.5 ml -
emulsion Test fuel
with additive B Il clear clear 2 ml 1st ml
emulsion

Note} Details on the composition of the fuels see previous table.

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As from the test results given in the first table shows the additive according to the invention alone and in conjunction with the high-boiling point Mineral oil component has better cleaning properties than commercially available additives at a comparable concentration in fuel j with a comparable effect, significantly lower amounts of additive according to the invention are obtained the end *

Table 2 shows that the fuel with the invention Additive is superior to fuels with conventional additives in terms of water-absorbing ability.

The technical progress of the additive according to the invention becomes particularly clear when the results of both Tables are viewed together.

-H- $ 09830/0923

Claims (1)

Patents claims Polyalkylene glycol polyamines of the general formula H-Γ 0-CHp-CHR ₁ ^ I- NEp —Fr ^ -NR, X- —I Z in the R ₂ , R, and R. Hydrogen atoms and / or polyalkylene glycol radicals of the general formula H -To-CH ₂ -CHR ₁ 4-, 1. R _{1 is} a hydrogen atom and / or a methyl group and Rc is a divalent, saturated, aliphatic hydrocarbon radical having 2-6 carbon atoms and χ has a value of 5-50 and ζ has a value of 1-4 ", obtainable either by reaction of a polyalkylene glycol "Consisting of a polypropylene glycol and / or a polyethylene glycol and / or a polypropylene / ethylene glycol of the general" formula H - £ 0-CH ₂ -CHR ₁ 4- OH - 15 -609830/0923 it in which R ₁ and χ have the abovementioned meaning, with hydrogen chloride in a molar ratio of about 1: 1 and then with a polyamine of the general formula -ρ E ₅ -MH -j- H, in which R ^ and ζ have the meaning given above, or by reacting propylene oxide or ethylene oxide or mixtures thereof with a polyamine of the above said composition, as well as fuels containing these polyalkylene glycol polyamines. 2. Polyalkylene glycol polyamines according to claim 1, containing polyalkylene glycol radicals with a mean Molecular weight from about 800-1,200. 5. polyalkylene glycol polyamines according to claim 2, Containing polypropylene or polypropylene / ethylene glycol residues with 5-20 propylene oxide units and 0-20 ethylene oxide units. 4. Fuels containing the polyalkylene glycol polyamines according to any one of claims 1 to 3, optionally along with a high-boiling mineral oil cut. 5. Fuels according to claim 4, containing ethoxylated fatty alcohols.