DE1248364B - Fuels for engines with spark ignition - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

Number:
File number:
Registration date:
Display day:

ClOl

German class: 46 a6 - 7

St 17808 IV a / 46 a6
May 10, 1961
August 24, 1967

The invention relates to fuels for spark ignition engines that contain an additive to prevent or reduce deposits in the delivery system of internal combustion engines with spark ignition.

Irregular idling and stoppages require frequent carburetor adjustments, and readjustment was problematic in certain respects for the machine maintenance service. These Problems arise particularly with the increase in tourist traffic in overpopulated areas and the Use of carburetors with many constrictions in private passenger cars. It was determined, that a primary factor in poor idling is the accumulation of debris in the section of the throttle of the carburetor, which is an over-rich mixture at idle and a reduction the idle speed. The accumulation of debris in the delivery system the engine and especially in the throttle section of the carburetor is particularly pronounced On journeys that require significant idling, such as powerhouses and door-to-door delivery services. In private car operations this problem occurs particularly in city traffic with considerable stopping and restarting.

The critical accumulation point for these deposits is adjacent to the throttle valve, whose Position controls the air-fuel ratio. As these deposits build up, the airflow is restricted at idle without changing the fuel supply, and it results a rich mixture that causes irregular idling and stoppage of the machine. Around to compensate for the presence of these deposits, the throttle must be opened slightly, by increasing the idle speed setting, which although a greater airflow can flow, automatically increases the fuel supply. This requires a correction of the fuel by changing the adjustment screw for the idle mixture to a compensating extent. That amount of idle adjustment required to maintain satisfactory idle performance is an indication of the rate of deposit formation. Furthermore Deposits often form in the idle air duct and cause constrictions that a Promote vacuum in the manifold so that more gasoline is drawn into the engine, thereby causing in turn, causing a rich idle and stalling of the machine.

Fuels for spark ignition engines

Applicant:

Standard Oil Company, Chicago, JIl. (V. St. A.)

Representative:

Dr. I. M. Maas, patent attorney,

Munich 23, Ungererstr. 25th

Named as inventor:

Robert Edward Malec, Chicago, JH. (V. St. A.)

Claimed priority:

V. St. v. America May 11, 1960 (28 245) - -

It has been discovered that the primary source of these deposits is contaminants in the supply air the machine are idling when working. The greatest source of this pollution in the Supply air is the machine's draft, which makes up about half of the deposits. The exhaust gases from other vehicles, dust and other components that are considered normal air pollutants are classified, contribute to the formation of deposits.

Surprisingly, new fuels for spark ignition engines have now been found that Prevent or alleviate precipitation in the delivery system of such machines, irregular Idling and stopping of such machines caused by the accumulation of deposits in the infeed system of such machines, prevent or remove deposits from the infeed system from internal combustion engines with spark ignition.

The fuels for spark ignition engines, which consist of a gasoline, are characterized by that they contain 0.0005 to 0.5% of a mixture of (1) a carbamate from the group hydroxylalkyl-3- (N-alkylamino) -propylcarbamate and hydroxyalkyl-3- (N-alkenylamino) -propylcarbamate of the general formula (I)

OR ¹ R ³

RNHCH0CH0CH0NHCOC COH

I I

R ² R ⁴

709 638/464

in which R is an acylic aliphatic hydrocarbon radical with about 8 to about 32 carbon atoms and R ¹ , R ² , R ³ and R ^{4 are} hydrogen, an alkyl radical with 1 to 4 carbon atoms, and (2) a substituted propylene urea of the general formula (II)

Il c

RN NH

HoC CH ₂

\ / CH ₂

in which R is an acylic aliphatic hydrocarbon radical with 8 to 32 carbon atoms, wherein the carbamate and the cyclic urea in said mixture in the weight ratio of 2: 1 to 1: 2 are present, and optionally contain a tetraalkyl lead as an anti-knock agent.

The radical R preferably consists of an alkyl group having from about 10 to about 20 carbon atoms which is derived from a fatty acid or mixed fatty acids. If R ¹ , R ² , R ³ and R ^{4 are} alkyl radicals, they can be the same or different.

Examples of suitable carbamates are:

HO

1. Ci ₈ H ₃₅ - N - CH ₂ - CH ₂ CH ₂ -NCO-CH ₂ -CH ₂ OH
2-hydroxyethyl 3- (N-octadecenylamino) propyl carbamate,

HO

2. Ci ₂ H ₂₅ - N - CH ₂ - CH ₂ - CH ₂ - N - C - O - CH ₂ - CH ₂ OH
2-hydroxyethyl-3- (N-dodecylamino) -propylcarbamate,

HO

3. Ci ₂ H ₂₅ - N - CH ₂ - CH ₂ - CH ₂ - N - C - O - C ₃ H ₆ OH 2-hydroxypropyl-3- (N-dodecylamino) propyl carbamate.

Suitable cyclic ureas are illustrated by the following examples:

1. Ci ₂ H ₂₅ -N NH

H ₂ C CH ₂

\ /
CH ₂

N-dodecylpropylene urea,

2. Ci ₈ H ₃₅ -N
H ₂ C

NH

CH ₂

CH ₂

Il c

3. Ci ₈ H ₃₇ -N

NH
CH ₂

CH ₂

N-stearyl or N-octadecyl propylene urea.

Even if combinations of the carbamates and cyclic ureas described in the defined Conditions are effective, they are not necessarily all equally effective in their effectiveness, since the specific activity of such mixtures can vary to an extent ranging from depends on the severity of the conditions of use and other factors.

When preparing fuels for engines with 65 spark ignition, the carbamate and the Urea can be added to the fuel individually in the stated amounts and proportions. N-oleyl or N-octadecenylpropylene urea, the carbamate and the urea can be

The desired ratio can be premixed and the mixture added to the fuel, or in situ A prepared mixture of carbamate and urea can be added to the fuel.

The mixture of carbamate and cyclic urea can conveniently be prepared in situ by having molar proportions of an N-alkyl- or N-alkenyl-1,3-propylenediamine and an alkylene carbonate at a temperature of about 50 to about 250 ⁰ C for a time reacts sufficient to give a reaction product containing a mixture of carbamate and cyclic urea in a weight ratio of about 1: 2 to about 2: 1, preferably in a molar value of about 1: 1. The response is represented by the following equation:

HHHHH
2R - - C - C - C - - H + 2R ¹ --C HHH R ²

O O

CR ⁴ R ³

HHHHHO

R ¹ R ³

(I)

(I) 2R —Ν —C —C —C —Ν —C —Ο —C —C — OH

HHH | j R2 R ⁴

HHHHHO R ¹ R ₃

R-N-C-C-C-N-C-0-C-C-OH
HHH R2 R ⁴

II R ² R ³

, Cs

(II)

RN Hv NH + Ri-CC-:
/ H OH OH

(III)

^{C C}

wherein R, R ¹ , R ² , R ³ and R ^{4 have} the above meaning.

The formation of the cyclic urea (II), a tetrahydropyrimidone, is a condensation reaction, the cleavage of a glycol molecule (III), which is the carbonate ester used as the starting material corresponds to, from which 3-aminocarbamate (I) includes. The secondary reaction under formation of the cyclic urea takes place much more slowly than the primary reaction with formation of the carbamate, thereby varying the reaction conditions to achieve the desired carbamate-urea ratio is facilitated. An extension of the reaction time and an increase in the reaction temperature favor the increased formation of urea at the expense of the carbamate yield. The distribution the products can easily be determined by infrared spectroscopy. This can cause the reaction be easily steered. When the desired reaction mixture is reached, the reaction is stopped, by cooling by means of suitable measures and a suitable solvent, for example Xylene and isopropyl alcohol, added.

For the manufacturing processes given below for some additional components of the invention No protection is claimed for propellants within the scope of the invention.

a) To 287 g (1.0 mol) of N-Coco-1,3-propylenediamine, 79 g (0.9 mol) of ethylene carbonate are added over the course of 3 ¹ IZ hours. The temperature is maintained throughout the reaction period at about 15O ⁰ C.

Heating is continued for another half hour at the same temperature. The carbamate-urea ratio of the product is 1.5.

b) To a refluxing mixture of 144 g (0.5 mol) of N-Coco-l, 3-propylenediamine and

187 g of xylene are 43 g (0.49 mol) of ethylene carbonate within 4 ¹ '; » Hours added. The carbamate to urea ratio of the product is 8.2.

c) To 144 g (0.5 mol) of N-Coco-1,3-propylenediamine, 43 g (0.49 mol) of ethylene carbamate are added within

added 4 hours, during which time the temperature is held at 17O ⁰ C. The carbamate to urea ratio of the product is 0.42.

d) To 81 g (0.25 mol) of N-oleyl-1,3-propylenediamine, 19.8 g (0.22 mol) of ethylene carbonate are added within a period of IV2 hours with stirring and Maintaining a temperature of 160 ° C

given. The carbamate to urea ratio of the product is 1.6.

e) To 144 g of N-coco-l ^ -propylendiamin be 39.6 g (0.45 mol) of ethylene carbonate added over 6 hours while stirring and maintaining the temperature at 50 ⁰ C. Heating and stirring are continued for an additional half an hour. The product is essentially pure carbamate.

f) To 144 g of N-Coco-1,3-propylenediamine, 39.6 g (0.45 mol) of ethylene carbonate are added with stirring over a period of 5 hours at 200 ° C. The intermediate product weighs 179 g. ^{100 cm 3 of} mixed xylenes are added to 135 g of this substance. The mixture is refluxed for 30 hours, 16 cm ^{3 of} ethylene glycol being removed as a xylene azeotrope. The end product after removal of the solvent weighs 113 g. The product consists essentially of pure N-coco-propylene urea.

g) To 316 g (1.1 mol) of N-coco-l ^ -propylendiamin 88 g (1.0 mol) of ethylene carbonate are added with stirring over a period of 3 * / ₂ hours at 140 ° C. The mixture is ^{heated for a further 6 3} Å hours at the same temperature. The product has a carbamate to urea ratio of 1.5.

h) 51 g (0.5 mol) of propylene carbonate added within a period from _^3/4 hours with stirring to 150 g (0.52 mol) of N-coco-l, 3-propylenediamine. The temperature is maintained at 150 ⁰ C. Heating and stirring are continued for an additional 5 hours. The product has a carbamate to urea ratio of about 1.

The N-Coco-1J-propylenediamine used above is a fatty series propylenediamine that has both a primary and secondary amino group has and the general formula

RNHCH2CH2CH2NH2

40

in which R is derived from the mixture of fatty acids resulting from the hydrolysis of coconut oil with 6 to 18 carbon atoms is obtained, which is obtained predominantly from fatty acids with 10, 12 and 14 carbon atoms consists.

The invention is illustrated in more detail by the following examples.

Examples

The effectiveness of the carbamate ring urea described in terms of preventing the Exposure due to carburetor deposits is illustrated by the data in the table. These Data were obtained by means of a so-called "Pontiac Carburetor Gum Test" (examination for content on resinous residues), which was carried out in the following manner:

A 1957 Pontiac engine equipped with a 4-funnel Rochester carburetor was used to conduct the test. A vacuum connection for manifold pre-ignition was applied in the throat area of the carburetor, which was normally in the region of atmospheric pressure at idle. As deposits formed on the throttle bore, it was necessary to open the throttle valve more in order to obtain the same air flow for the same number of revolutions. When this was achieved, the connected vacuum was partially in the vacuum area of the manifold. At the beginning of the experiment the vacuum at the connection was about 50.8 to 76.2 mm Hg. The failure point of the experiment was considered to have been reached when this vacuum increased by about 203.2 mm Hg, ie when the connection vacuum was 254.0 to Reached 279.4 mm Hg. In order to tighten the test conditions, all draft of the crankcase and some of the exhaust gases were fed to the carburetor. The time to failure for the base fuel (control), that is, the time it took to increase the vacuum by 203.2 mm Hg using the control fuel, was about 20 hours. During the test, the machine worked in a 3-minute cycle of 2% minutes at 500 rpm. idling and ¹ rpm at 1600 rpm. without burden. The opening of the throttle and the mixture settings were carried out, if necessary, every hour to keep an idle speed of 500 rpm. maintain. The combustion factor is calculated as follows:

Time required for failure with fuel + additive ₌ improvement factor Time required for failure with basic fuel

The test results are expressed as the "improvement factor" as defined above. The motor fuel used was a commercially available branded gasoline with the usual additives, d. H. Tetraethyl lead, detergents, antioxidants, metal passivants, contained.

fuel

fuel

No. 1 + 24 parts per million
Product of a)

No. 1 + 24 parts per million
Product of b)

Improvement factor

1.0

5.7 4.0, 3.5
(Mean value 4.4)

1.0

55

60

sample
No. fuel Improvement
factor 4th No. 1 + 24 parts per million 2.0 Product of c) 5 No. 1 + 24 parts per million 3.6 Product of d) 6th No. 1 + 24 parts per million 1.0 Product of e) 7th No. 1 + 24 parts per million 2.0 Product of f) 8th No. 1 + 12 parts per million 4.5 Product of e) + 12 parts per million Product of f)

continuation

fuel

No. 1 + 8 parts per million
Product of e)
+ 16 parts per million
Product of f)

No. 1 + 16 parts per million
Product of e)
+ 5 parts per million
Product of f)

No. 1 + 12 parts per million
Product of g)

No. 1 + 16 parts per million
Product of g)

No. 1 + 24 parts per million
Product of g)

No. 1 -f 24 parts per million
Product of h)

Improvement factor

3.3

2.5

2.0

3.1, 3.0
(Mean value 3.05)

3.4 3.5

In addition to the above experimental data, fuels for spark ignition engines according to the present invention have been developed subjected to extensive tests in laboratory machines and on driving routes. In the laboratory, the fuels containing the carbamate-urea mixture according to the invention the Chevrolet Introductory System Deposition Test (ISD), the CFRL Nead Surface Ignition Test and the spark plug contamination test. Furthermore, the mixture described showed no adverse effects on the initial or storage stability of the fuel. Fuels with the carbamate-urea mixture described were in a lot of powerhouses about a extended period of time under regular control of the delivery systems, especially the carburetors the test cabs checked on routes. In this test it was observed that the invention Fuels prevented deposits in the delivery system as well as existing ones Effectively removed deposits. As a result, the cabs that were equipped with the invention Fuels, ongoing satisfactory maintenance extending beyond the periods after which carburetor adjustments or overtaking could normally be expected.

Fuels according to the invention which contain the carbamate-urea mixture described here, known antioxidants, stabilizers, anti-freeze agents, anti-knock agents, Cleaning agents and / or other additives commonly used in fuels for engines Spark ignition can be used.

The propellants according to the invention with a content of tetraalkyl lead anti-knock agents, such as tetramethyl lead, Tetraethyl lead and / or mixtures thereof, are described by the addition of the here Carbamate-urea mixture increased in its effect.

The propellants according to the invention can contain tetraalkyl lead corresponding to a concentration of about 0.132 to about 1.32 cm ³ / l of the propellant or more.

Information about percentages relate to the weight, unless otherwise stated.

Claims (1)

Claim: Fuels for spark ignition engines consisting of a gasoline thereby characterized in that it contains 0.0005 to 0.5% of a mixture of (1) a carbamate Hydroxyalkyl-3- (N-alkylamino) -propylcarbamate and hydroxyalkyl-3- (N-alkenylamino) -propylcarbamate group of the general formula (I) OR ¹ R3 RNHCH ₂ CH ₂ CH ₂ NHCOc COH I R ² R ⁴ in which R is an acyclic aliphatic hydrocarbon radical having about 8 to about 32 carbon atoms and R ¹ , R ² , R ³ and R ^{4 are} hydrogen, an alkyl radical having 1 to 4 carbon atoms, and (2) a substituted propylene urea of the general formula (II) Il c RN NH • 'V, V ~ X12 CH ₂ in which R is an acylic aliphatic hydrocarbon radical with 8 to 32 carbon atoms means, the carbamate and the cyclic urea in the mixture mentioned in a weight ratio from 2: 1 to 1: 2 are present, and optionally contain a tetraalkyl lead as an anti-knock agent.