CZ35192A3 - Derivatives of dicarboxylic acids as additives in low-lead or lead-free petrols - Google Patents

Abstract

The derivatives have a structural chemical formula I <CHEM> where R1 is a bivalent hydrocarbon functional group or hydrocarbon functional group with nitrogen atoms in amino-position and/or etheric position with total number of carbon atoms from 1 to 38, R2 is a monovalent hydrocarbon functional group with a number of carbon atoms from 1 to 42 or hydrogen, X is a hydrogen and/or alkaline metal and/or alkaline earth metal, Y is oxygen or nitrogen, a and b are cardinal numbers zero or 1, selected such that a + b >/= 1, R3 is hydrogen or a monovalent hydroxy-substituted hydrocarbon functional group with a number of carbon atoms from 1 to 42 or a monovalent hydrocarbon functional group with a number of carbon atoms from 1 to 42 or a monovalent functional group of structural chemical formula II or III or IV, -[-CH2)c-NH-]dR4 (II) <CHEM> <CHEM> where R4 is hydrogen or a monovalent hydrocarbon functional group with a number of carbon atoms from 1 to 42 or a functional group of structural chemical formula III, R5 is hydrogen or a monovalent hydrocarbon functional group having a number of carbon atoms from 1 to 3, R6 is hydrogen or a functional group <CHEM> c is a cardinal number from 1 to 10, d is a cardinal number from zero to 6, e is a cardinal number from 1 to 50, f is a cardinal number from 1 to 50.

Description

(57) Derivatives of dicarboxylic acids as additives to low-lead or unleaded motor gasolines, which prevent wear on the exhaust valve seats of cars not designed to burn unleaded gasoline. The dicarboxylic acid derivatives according to the invention have the structural chemical formula (I).

coox /

what (R ^)

4- 3 (I) (R-b)

J 'Ί of x1

- - <

l ΠΊ \ ί i.h.0 cl C V n CttčjoO ', /

Dicarboxylic acid derivatives as additives to unleaded motor gasolines

Technical field

The present invention relates to automotive wear additives as dicarboxylic acid derivatives, such as low-lead or gasoline, by virtue of which the exhaust valve seats are not structurally adapted to the gasoline.

combustion of oezoiovnatycn is prevented in unleaded cars

BACKGROUND OF THE INVENTION

The trend towards the use of unleaded gasoline is remarkable in the whole education scale as a result of efforts to bez lead a healthier environment to lead-free. The US started with gasoline at the beginning; n

In Japan, unleaded petrol started to be produced in 1974 and

Surope at the beginning of 1984. Since then, its share in the production and consumption of gasoline has been rising sharply. The global trend thus clearly leads to the production and use of only unleaded gasoline. For example, since March 1986, only unleaded petrol has been used exclusively in Japan [1,2]. In the USA, the share of total production in 1990 was 90%, and in the early 1990s it is considered to completely exclude the production of leaded petrol. In Surope, given the time lag and the diversity of the car fleet and the technical possibilities of the refineries, the situation is not as clear as it is overseas. Unleaded petrol is finding its place on the market in different countries at different speeds.

In advanced European countries, the share of unleaded gasoline production in total production as well as gasoline is currently around 50¾. The total production of unleaded gasoline is estimated to be at least 75 ó in 1995 [3,4], compared to 21,3¾ in 1936 and 26¾ in 1987 [5,6]. Unleaded petrol has been produced and handed over in Czechoslovakia since 1986. In 1990 its share in total production! elderberry did not exceed 3¾.

The production and distribution of unleaded gasoline from the beginning encounters a major problem which, together with the technical capabilities of refineries, is the main brake on the immediate transition to the production and use of unleaded fuel only. This problem is the impossibility of burning unleaded gasoline in cars constructed on leaded fuel. The burning of unleaded gasoline in such cars results in damage to the cylinder head of the engine to the engine itself and to the decommissioning of the car [7-12]. It is basically an old-fashioned problem that car manufacturers encountered in the early 1920s, which suddenly solved when lead-based anti-knockers were added to gasoline. The number of cars at risk of burning unleaded gasoline has been estimated to be 70 million worldwide by 1987 [10], of which around 7 million in the UK [13]. In the CSFR, the number of cars unable to use unleaded fuel is estimated to be around 70¾ of the total number of passenger cars, and due to the statistically determined 5¾ - year replacement of passenger cars in the CSFR per year it is expected to disappear only around 2010 [7,8].

Almost all cars manufactured by 1971 belong to this group of cars [10]. On the other hand, most automakers, since 1936, have been producing models capable of burning unleaded gasoline [14,15],

The cause of engine failures in the combustion of unleaded fuel in these cars is the quality of the material from which the unleaded wear.

Exhaust valve seats, resp. the entire engine cylinder head. If these are of cast iron or the like, rapid abrasion occurs during combustion; and

As a result, the exhaust valves become more and more recessed into the cylinder head of the engine, and the valve steer is thereby constantly reduced. The final stage of this process is imperfectly closing the combustion chamber, loss of compression and engine power, tanning of exhaust valves and their seating. Finally, the engine cylinder head is destroyed [10,12].

The degree and speed of the seating of the exhaust valves depends on the design and operating parameters of the car. In addition to the hardness of the seat material, the design parameters include valve rotation, spring tension, seat angle and width, operating temperatures and valve geometry. The most important of the operating parameters are the engine speed, its load and the richness of the fuel-air mixture. Valve rotation. high engine speed and load and lean mixtures have a drastic effect on the seating of the exhaust manifold [10,12].

Practically only in the twilight of the use of lead compounds in gasoline, it turned out that, in addition to increasing the detonation stability, lead in gasoline performed another very important function of protecting the exhaust valve seats from mechanical wear during engine operation. It is believed that the combustion products of lead anti-knockers form a thin protective film on the valve seat surfaces, preventing high temperature oxidation and abrasion, and reducing adhesion and material transfer. thus protecting them from unwanted wear and tear [10],

The solution to the problem that would result in the power to use unleaded fuel in this endangered group of cars is:

and / replacing the cylinder heads of these automobiles with heads with specially cured exhaust valve seats; which is virtually impossible and financially unacceptable to many run-off types, b / adding to lead-free petrol such as a harmless additive to catalyze harmless additives that would replace the film-forming function of lead compounds and provide the exhaust valve seats with the necessary protection. Only two kinds of ingredients of this designation are currently offered on the world market. Although functionally satisfactorily satisfying several foreign engines, ŠKODA engines failed to provide effective protection against the bore of their exhaust seats, even at several times as much as recommended by the manufacturer [8].

Another option is to use leaded petrol until such vehicles are represented in the fleet, which however makes it possible to produce and use only unleaded petrol with the consequent negative environmental impact.

Li teratúra

1. Chem.Econ. and Eng.Rev., 9, 25 (1986). 2. Chem. Ind., 7, 750 (1986). Third Oil and Gas Journal 88. 4. 11 (1990). Λ Zrdol and Kohle. 3. 119 ( 1988). 5. Oil and Gas Journal. 85. · 14. 15 (1987) 6. Fetrole et Techniques, 38 , 316 (1986):

i2

Bratsky.D., Oravkin.J. : Production of gasoline in Czechoslovakia at the turn of the millennium, 33.Konferencia o ropě, 1988.

Fehér.P., Oravkin.J., Málach.V. : Trend in the development of automotive petrol and additives. Studies. VORUP, Bratislava, 1990.

60, 326 (1986).

95, 11, 72 (1987).

Bratislava

Bratský.D.

Petrole et Tecnniques, Kydrocarbon Processing,

68, 7, 11 (1989).

Grill.R.A., - Landells.R.G.M.

The Reduction of Leads in Gasoline and Its Effect on Valve Seat Recession The Problem and Its Solution., Proceedings of the 33rd Conference on Oil with Foreign Participation, Bratislava, 1988. Hydrocarbon Processing. 68, 7, 17 (1989).

Autozeitung, 20, 67 (1989).

Autozeitung, 21, 66 (1989).

SUMMARY OF THE INVENTION

The most preferred solution to this is the use of only unleaded gasoline containing dicarboxylic acid derivatives of the present invention. Their addition when completely unleaded or non-leaded from combustion ensures that low-leaded gasolines damage the exhaust valve seats of unhardened materials of various types, e.g.

The dicarboxylic acid derivative additives described in this invention are harmless to health and harmless to catalytic exhaust gas converters.

The d-carboxylic acid derivatives according to structural chemical formula I:

of the invention have /

and (I) in which it represents a divalent hydrocarbon function or a hydrocarbon function with nitrogen atoms in the amino group and / or oxygen atoms in the hydroxy and / or ether group with the total

the number of carbon atoms from 1 to 38.

R2 is a monovalent hydrocarbon function having from 1 to 42 carbon atoms or hydrogen,

X hydrogen and / or an alkali metal and / or alkaline earth metal group,

Y oxygen or nitrogen, a and b integers zero or 1, with a + b> 1,

R @ 1 is hydrogen, or a monovalent hydroxy-substituted hydrocarbon function of 3 by a number of carbon atoms of 1 to 42. or a monovalent hydrocarbon function of s. the number of carbon atoms from 1 to 42, or a monovalent functional group with structural chemical formulas II or III or IV, (Cn.

-NH-] (II) (III) - (-CH-CH-O-) -R 1, β 2 (-CH-CH-O-) - CH-CH-1-NH 2 e-1,2 < ^CH 2> c- ^J d- ^N (IV) in which is

R @ 1 is hydrogen or a monovalent hydrocarbon function having from 1 to 42 carbon atoms or a functional group having structural chemical formula III,

R 8 is hydrogen or a monovalent hydrocarbon function having a carbon number of 1 to 3.

R 8 is hydrogen or a functional group

- (- CH-CH ₂ -O-) _f -H

C the whole number from i to 10th D the whole number from zero to 6 e the whole number from I to 50. F the whole number from 1 to 50th

The acids applied in are potent inhibitors

Such dicarboxylic unleaded automotive gasoline derivatives wear out the exhaust valve seats of cars not designed to burn unleaded auyobenzines, thereby allowing them to be continuously fed to the fuel.

To improve; manoulation. in particular, viscosities and thus pumpability at the stage of filling into containers, transport and application of dicarboxylic acid derivatives as additive to gasoline according to the invention may also contain an auxiliary component which is an organic solvent of the preferred aromatic type. Suitable solvent types are toluene, xylene, aromatic hydrocarbons having from 9 to 13 carbon atoms in the molecule, or technical mixtures such as the naphtha reformate, the reformate fraction boiling in the range of 75 ° C to 250 ° C, the fraction from pyrobenzine with a similar rain range. The aromatic hydrocarbon content of these mixtures is usually above 25% by weight.

In order to ensure the above-mentioned effects of the dicarboxylic acid additives according to the invention, they are added to the gasoline at a concentration of from 0.025 to 1.1% by weight. If the additive according to the invention also contains an auxiliary component, which is an organic solvent as specified above, then the resulting addition of the additive to the autobenzine is chosen such that the concentration of the active ingredient is within the stated range.

In order to improve the pumpability and also to maintain the required content in the gasoline, the additive according to the invention can be diluted directly with the gasoline before it is added to the gasoline. or a hydrocarbon solvent thereof.

The additive according to the invention can be added to the gasoline either directly at the stage of preparation of the gasoline in the refinery (primary addition) or it can be added to the finished gasoline at the stage of its consumption or distribution, for example at petrol stations (secondary addition). The secondary addition of the additive according to the invention is advantageous, in particular in cases where the automobile gasoline is produced without its content.

DETAILED DESCRIPTION OF THE INVENTION

The following examples illustrate the advantages and practical use of the specified dicarboxylic acids as additive to the gasoline of the invention, but without limiting the scope of the invention in any way.

Example 1

A 4-cylinder petrol engine with a cylinder capacity of 1174 cm with a cast iron cylinder head was subjected to a site engine test under the conditions of Table 1 using total unleaded petrol (0.0000 g Pb / l) with an octane rating of 96 by the research method; 87 as well as unleaded petrol containing a lead concentration for unleaded petrol. i 0.013 g Pb / 1 with the same octane level. During the test, the valve oxides were measured every 6 hours and, if necessary, adjusted to a minimum value of not less than 0,2 mm. At the end of the 36-hour engine test, the engine cylinder head was removed from the intake and exhaust valves. After detecting the change in weight of the valves, the overall depression of the exhaust valve seats was measured. The results obtained are shown in Tables 2 and 3, in which the individual values represent both the magnitude of the average recess of the 4 rollers and the values for one, the most recessed roller. The results of the test showed that the use of unleaded gasoline is not possible with this type of engine.

A similar test was also performed with said totally unleaded autobenzine (0.0000 g Pb / l), but containing 850 ppm of the dicarboxylic acid derivative according to the invention with chemical structural formula (I). where is the

Y is nitrogen, R J ^is hydrogen.

b = 1, R is - [- (CH 2) -NH -], - R. 2 cd 4 wherein c = 2 ^and 4 polypropenyl having an average molecular weight of 450 g / mol.

The dicarboxylic acid derivative was prepared by reacting phthalic anhydride with N-polypropenyl-diethylenetriamine and then neutralizing the resulting phthalic acid derivative with calcium oxide.

The results of this test showed that no exhaust valve seats were clogged on any engine cylinder, even if the test duration was extended to 56 hours (average change in exhaust valve valve clearance was -0.0075 mm, maximum measured value -0.04 mm).

Example 1 and d 2

The four-engine petrol engine damage type 742,13 with 1 lathe cylinder head was tested for long-term engine life test (300 hours) under conditions according to UN 30 0506, using unleaded petrol with octane number 96 research method and 37 engine method ( 0.004 g Pb / l). The fuel used was saturated with 700 ppm of an additive according to the invention of structural chemical formula (I), wherein X is sodium, Y is oxygen. and is zero.

is -f-ON-CH -ΓΗ-ΓΗ. where e = 3-5

and Rg is

- (- CH - CH-O -) - H

^LH 3 wherein f

The dicarboxylic acid derivative was prepared by reacting tetrapropenyl succinic anhydride with propoxylated tetradecylamine and subsequent neutralization of the formed intermediate with sodium hydroxide.

The additive of this composition was dissolved in the naphtha reformate prior to addition to unleaded autobenzine so that the resulting solution contained 50% active ingredient.

The results of this test showed that none of the engine cylinders had exhausted the exhaust valve seats (the average change in the exhaust valve bee was 0.055 mm). Unleaded gasoline containing the aforementioned additive according to the invention fully protected the exhaust valve seats of the used engine while not deteriorating any of its operating parameters and did not reduce its overall service life.

Example 3

The fleet presented in Table 4 also carried out honorary engine tests of 50,000 to 80,000 kilometers. New engines, carburetors, fuel tanks and intake manifolds are used in cars. Unleaded gasoline (0.001 - 0.005 g Pb / 1) with OCVM 95 - 97 containing ΜΤΞΞ 7 - 12% vol. . which has been additivated with 750 ppm of a dicarboxylic acid derivative according to the invention with structural chemical formula (I) in which

R 1 is -CH = CH-, X is sodium, Y is nitrogen, R ₂ is phenyl-, a = 1, b = 1. R ₃ is ^C 12 ^H 25 -

Said dicarboxylic acid derivative was prepared by reaction of the corresponding secondary amine with maleic anhydride followed by neutralization of the resulting intermediate with sodium hydroxide.

The additive of this composition was dissolved in an aromatic solvent boiling from 14 ° C to 190 ° C prior to addition to unleaded autobenzine such that the resulting solution contained 10% active ingredient.

All vehicles were driven mainly in urban and highway traffic during the tests. After every 5,000 km, it was checked along the exhaust valves, and every 10,000 km were measured for the performance and emission characteristics of the vehicles, as well as their fuel economy and octane demand. The efficiency of vehicles with catalytic converters was determined. At the end of the tests, the engines hurt dismantled and comprehensively evaluated.

Evaluations have shown that exhaust valve seats provide complete protection against unleaded gasoline. no ignition function harmless to catalytic gases and does not worsen emissions;

The additive according to the invention provides all tested cars with combustion wear The additive does not affect the negative engine or its service life. It is the systems of refinement of the exhaust genie engine.

Table 1

Site engine test conditions

phase

Test cycle composition

Duration Engine speed [min] [l.min]

Engine load

1. 20 3000 full 10 550 idle Third 20 5000 full 4. 10 650 idle

Table 2

Effect of test duration on exhaust valve seat bore using lead free gasoline (0.000 g Pb / 1) and additive free according to the invention

Count hours Depression of exhaust valve seats [mm diameter for 4 cylinders one cylinder max. 12 0.26 0.35 24 00:45 0.60 36 0.30 1.19

Table 3

Effect of test duration on exhaust valve seat bore using 0.013 g Pb / l of lead gasoline and additive-free according to the invention

Number of exhaust valve seats [mm] hours diameter per 4 cylinders one cylinder max.

0.12 0.23 24 0.32 0.54 36 0.43 0.76

Table 4

Car fleet used for honor engine tests

Vehicle type

Number of vehicles1

SKODA 120 3 IT IS A PITY 130 L 8 IT IS A PITY FAVORIT 136 L with catalytic converter -4 VOLGA GAZ 24.10 2 OLTCII  11 R about

Industrial applicability

The application of the dicarboxylic acid derivatives according to the invention to unleaded gasoline permits the continuous trouble-free operation of all petrol-engined vehicles on this more environmentally-friendly fuel and thus allows virtually instantaneous transition from leaded gasoline to the production and use of unleaded fuel only.

Claims (1)

PATENTOVÉ ν'a r'o k y Dicarboxylic acid derivatives as additives to low-lead or unleaded automotive gasoline, which prevent wear on the exhaust valve seats of cars not designed to burn unleaded gasoline, characterized by having the structural chemical formula I: and (I) ^(R 3b) wherein R 1 is a bivalent hydrocarbon function or a hydrocarbon function with nitrogen atoms in the amino group and / or oxygen atoms in the hydroxy and / or ether group with a total number of carbon atoms from 1 to 38, A single monovalent hydrocarbon function having from 1 to 42 carbon atoms or hydrogen, X hydrogen and / or an alkali metal and / or alkaline earth metal group, Y is oxygen or nitrogen, and a and b are integers of zero or 1, with a + b> 1. hydrogen, or a monovalent hydroxy-substituted hydrocarbon function having a carbon number of from 0 to 42, or a monovalent hydrocarbon function having a carbon number of from 1 to 42, or a monovalent functional group with structural formulas II or III or IV, - [- (CH ₉ ) -NH -], - R, ZC d 4 (II) (III) (-CH-CH-O-). -CH-CH- [-NH- (CH 2) -J] -N-R 2 = 1, 2 zcd, 2 (IV) wherein is R @ 1 is hydrogen or a monovalent hydrocarbon function having from 1 to 42 carbon atoms or a functional group having structural chemical formula III, R @ 1 is hydrogen or a monovalent hydrocarbon function having from 1 to 3 carbon atoms, R- hydrogen or the functional group - (-CH-CH3, -O-), -H C integer from 1 to 10. D integer from nu I a to 6 £ integer from 1 to 50. F integer from 1 to 50.