DE2456598A1 - ENGINE GASOLINE AND ADDITIVE - Google Patents

Description

EGG. DU PONT DE NEMORS AUD COMPANY 10th and Market Streets, Wilmington, Delaware 19 898, V.St.A.

Motor gasoline and gasoline additives

The invention relates to improved gasoline with good anti-icing, Anti-rust effect and cleaning effect for the carburetor and the lower engine compartment.

Uneven idling and stalling of the engine are known Difficulties encountered with automotive carburetor spark ignition engines. One of the causes of the uneven Idling and stalling is the build-up of debris on the carburetor throttle and the surrounding ones Walls. The build-up of debris disrupts normal airflow in the carburetor, creating fuel-rich mixtures form. The deposits can be caused, for example, by the accumulation of impurities in the air, by blowing past (blowing through) in the engine and caused by dust. Remedial action are periodic cleaning of the carburetor, which is costly, or increasing the normal idle speed of the engine, which makes the vehicle more difficult

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drives, and means a waste of fuel.

Other difficulties can arise with the engines of currently manufactured automobiles, particularly during the warm-up period of the engine, and these difficulties manifest themselves in frequent stops, in irregular Engine idling and reluctant to start. It has been recognized that these difficulties are due to various amendments of the engine and the additional devices that have the task of controlling the content of the To keep exhaust gases of hydrocarbons, carbon monoxide and oxides of nitrogen under control. These difficulties can be caused by the operational difficulties mentioned at the beginning, which are due to the accumulation of deposits in the carburetor are based, to be reinforced. .. '

It is known that the formation of deposits in the carburetor can be reduced or completely prevented when using fuels which contain certain additives known as carburetor cleaners (carburetor detergents). Although the Effectiveness of such additives does not depend on a cleaning effect needs to be based, it is a fact, that these additives have both a cleaning effect on a carburetor in which there are already accumulated deposits, as well as keeping a clean carburetor in a clean condition. There are many known carburetor cleaners. These include long chain amines, amine phosphates, amides, amino amides, and amine carboxylates. The most effective types of compounds are the amine phosphates either alone or in combination with other additives. However, one recognizes to an increasing extent that the salary of fuels to phosphorus compounds is undesirable because the phosphorus has a harmful effect on the devices to control the exhaust gases that are installed in motor vehicles today. Hence there is a need for an effective carburetor cleaning additive for motor fuels that does not contain phosphorus.

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In addition to additives to keep the carburetor clean, they need Today's motor fuels still have other additives to improve their behavior, e.g. additives for rust protection, for the Anti-icing protection and to combat the formation of deposits in the intake system for reasons of easier handling and economic efficiency, the desired effect should be achieved with the lowest possible number of additives, and these additives are said to be effective even at low concentrations. Preferably one additive should have multiple effects have, i.e. it should be a multipurpose additive. While numerous multipurpose additives are known, many of them are but not usable, either because they have undesirable side effects or because they are used in too large quantities have to be if they are to have the desired properties.

The invention has for its object to provide a phosphorus-free additive for motor fuels available as Multipurpose additive works by providing anti-rust, anti-icing and cleaning properties for the carburetor and the lower engine compartment offers. The task is also to provide a motor fuel that has such a mult.ifunctional Has an effect. ■

The subject of the invention is a motor gasoline of .guter anti-icing and anti-rust effect and cleaning effect for the carburetor and the lower engine compartment on the base a hydrocarbon mixture boiling in the gasoline range, which is characterized in that it is a generally liquid, acylated polyalkylenepolyamine that is practically free of nitrogen-containing cyclic groups and is the general formula

OH · ·

R.-S ^ - (C _n H ₂

0, in which R is hydrogen and / or R'-C-, R 'has a seed

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saturated or unsaturated aliphatic hydrocarbon radical with 9 to 21 carbon atoms mean, η the value 2 or 3> and χ has a value of 2 to 6, in an effective amount, usually in an amount of 0.002 Ms 0.02 percent by weight, based on the hydrocarbon mixture contains.

The acylated alkylene polyamines used according to the invention can be completely acylated, ie each nitrogen atom of the polyamine can have an acyl substituent, or the polyamine can be partially acylated, ie only some of the nitrogen atoms of the polyamine need to have acyl substituents. If there are multiple acyl groups, it is believed that the terminal nitrogen atoms of the polyamine molecule contain acyl substituents. Alkylenepolyamines which are suitable for the preparation of the acylated polyamines have the general formula HgN- (C Hg _n NH) _x H, in which η and χ have the above meanings. When η is 3, C _n H _{2n can be} a 1,2- or a 1,3-propylene group. The alkylene polyamines and their preparation are known per se. For example, a suitable alkylene polyamine can be prepared by reacting a corresponding alkylene dihalide with ammonia. Representative known amines are diethylenetriamine, triethylenetetramine, tetraethylene pentamine, pentaethylene hexamine, dipropylene triamine, tripropylene tetramine, tetrapropylene pentamine and pentapropylene hexamine, all of which are commercially available. Mixtures of alkylene polyamines can also be used to prepare the acylated polyamines. Polyethylene polyamines are particularly preferred because of their ease of availability.

The alkylene polyamines can be acylated by reacting the polyamine with a carboxylic acid (because of the lower cost and easy availability preferred) of the general formula R'COOH, in which R 'has the above meaning, or an anhydride or acid halide of such a carboxylic acid according to known ones Process implements. Although a carboxylic acid is used in the description below, instead of

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^% i

anhydrides and acid halides can also be used.

The carboxylic acid used to acylate the polyamine is an aliphatic hydrocarbon monocarboxylic acid having 10 to 22 carbon atoms; it can be saturated or unsaturated be. This subheading includes alkane carboxylic acids, alkene carboxylic acids and alkadiene carboxylic acids. Carboxylic acids, in which the hydrocarbon part of the molecule is straight-chain, are preferred because they are generally less harsh reaction conditions for require acylation. Representative carboxylic acids are decanoic acid, decenoic acid, dodecanoic acid, dodecenoic acid, tridecanoic acid, Tridecenoic acid, tetradecanoic acid, tetradecenoic acid, hexadecanoic acid, hexadecenoic acid, octadecanoic acid, octadecenoic acid, Octadecadienoic acid, eicosanoic acid, uneicosanoic acid and doeicosanoic acid. Mixtures of acids can also be used, -and such acid mixtures are used because of their * lower cost, their better fluidity and their higher solubility preferred * Acid mixtures such as those obtained by saponifying natural fats and can be used Oils received. These include those made from coconut oil, corn oil, cottonseed oil, Acids derived from tallow and soybean oil. The acids made from tallow are usually mixtures of tetradecanoic acid, Tetradecenoic acid, hexadecanoic acid, hexadecenoic acid, Octadecanoic acid, octadecenoic acid, octadecadienoic acid and eicosanoic acid. The acids made from soybean oil are mixtures, the hexadecanoic acid, octadecanoic acid, octadecadienoic acid and eicosanoic acid. Those made from cottonseed oil Acids are mixtures that are usually tetradecanoic acid, hexadecanoic acid, octadecanoic acid, octadecadienoic acid, and eicosanoic acid contain. The acids obtained from coconut oil contain decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, Octadecanoic acid, octadecenoic acid and octadecatrienoic acid and a very small amount of octanoic acid. A particularly advantageous and preferred acid mixture are tall oil fatty acids, the are obtained from tall oil. Tall oil is a mixture of pine resin and fatty acids that are set free when the black liquor soap is acidified, those of the black liquor of the

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Sulphate process is skimmed off in the manufacture of Kraft paper. Crude tall oil is usually broken down into different fractions by distillation, in which the ratio of fatty acids to rosin acids varies in the range from 1:99 to 99: 1. In the context of the present description, the term tall oil fatty acid includes tall oil mixtures which have a fatty acid content of at least about 50 percent by weight and the remainder mainly consists of pine resin acids in a mixture with smaller amounts of unsaponifiables of unknown chemical composition. The fatty acids in tall oil fatty acids consist mainly of oleic acid, linoleic acid, conjugated linoleic acid, palmitic acid, stearic acid, palmitoleic acid, arachidic acid and behenic acid. Tall oil fatty acids that are commercially available include those with the following compositions: palmitic acid (0.1-5.3 $), palmitoleic acid (0.1-2.1 $), stearic acid (2.1-2.6 fo) , Oleic acid (39.3-49.5 #), linoleic acid (38.1-41.4 #), eicosanoic acid (1.2-1.9 $>), eicosadienoic acid (0.5-3.2 ^), Eicosatrienoic acid (0.4-2.9 °) and behenic acid (0.4-0.9 °) , the remainder pine resin acids, unidentified acids and unsaponifiables.

The acylated polyamines can be prepared by known methods will. If an anhydride is used as the acylating agent, the anhydride is mixed with the amine and heated the mixture mildly. If preferred, a catalyst such as pyridine can be used. When an acid halide is used as acylating agent, the acylation according to the known Schotten-Baumann reaction in the presence of aqueous alkali. If a carboxylic acid is used as the acylating agent, it is preferred The method consists in reacting the carboxylic acid with the polyamine at 70 to 200 ° C. in the absence of a solvent and no more than 1 mole of water of condensation per mole of reacted Remove acid. The ratio of carboxylic acid to polyamine in the reaction depends on the particular polyamine and the specific product you want. · It can be in the field

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from 1 mole of carboxylic acid per mole of polyamine "to 1 mole of acid each g atom of nitrogen per mole of polyamine vary. The preferred one acylated polyamine is made from tall oil fatty acid and tetraethylene pentamine produced in a molar ratio of .3ϊ1.

If you react a carboxylic acid with an alkylene polyamine, so under certain reaction conditions, especially when using an ethylene polyamine or a propylene polyamine, a cyclization reaction takes place in which the primary amino group, its neighboring amino group and the carboxyl group participate, and in which cyclic nitrogen compounds are formed which (if an ethylene polyamine is used) Imidazoline derivatives or (if a propylene polyamine is used) tetrahydropyrimidine derivatives. The acylated Polyamine compounds used according to the invention, are practically free of such cyclic, nitrogen-containing groups. Under "practically free of cyclic, nitrogen-containing groups "it is understood that the acylated polyamine has less than about 5 weight percent imidazolinode-r Contains tetrahydrqpyrimidine compounds. If the acylated polyamine by reaction of an anhydride or Acid halides are produced, and especially when such a reaction is carried out at a sufficiently low temperature, e.g. below about 150 ° C, generally arise no cyclic nitrogen compounds. When a carboxylic acid and a polyamine react, the formation avoided by cyclic nitrogen compounds if the reaction is carried out in the absence of a solvent, the Keeping reaction temperature below about 200 ° G and removing of condensation water to a maximum of 1 MbI of water each Molecular carboxylic acid converted. The cyclic nitrogen compounds differ in their action from the acylated polyamines, although both types of compounds are obtained by reacting the same carboxylic acid with the same alkylene polyamine are made in equal proportions and the only difference is that the cyclic

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Nitrogen compound in a solvent, whereas the acylated polyamines are produced in the absence of a solvent will. As will be shown below, the compounds of the latter type act as engine cleaners (by keeping the sludge formation low and the piston skirts keep clean) and react to the addition of opacifying agents, while the cyclic nitrogen compounds (e.g. inidazoline derivatives) are not used as cleaning agents for the engine act and do not react to opacifiers.

The acylated polyamines described above are particularly suitable as additives for hydrocarbon fuels Motor fuels that boil in the gasoline range and give them multifunctional properties as cleaning agents for the carburetor and the lower engine compartment, as a rust preventive and to a certain extent also as an anti-icing agent. Their Value and Suitability as Multipurpose Gasoline Additives is through the. additional properties of good resistance to extraction by water and against emulsion formation and a good response to opacifiers. To take advantage of the multi-purpose properties of the acylated To take advantage of polyamines, they are added to gasoline in concentrations from 0.002 to 0.02, preferably from 0.003 to 0.01 and in particular from 0.004 to 0.008 percent by weight added. The addition of more than 0.02 percent by weight means misuse of the additive because it does not provide any further benefit.

Since the acylated polyamines are generally liquids, they are well suited for easy addition to motor fuels in the oil refinery. Such an additive can be used by anyone in the art for the addition of liquid agents to motor fuels known method. Preferably, the acylated polyamines are in the form of a solution in a suitable one Solvents such as methanol, ethanol, propanol, butanol, benzene, toluene and xylene, or a mixture of several this solvent, before. The solution can contain the acylated poly-

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amine in concentrations of 10 "to 90, preferably 30" to percent by weight. To such a solution, which can be regarded as an additive concentrate, one can add an opacifier, which increases the ability of the fuel to separate from water, and an anti-icing agent, the latter providing the carburetor with increased anti-icing protection. Typically V / else can concentrate on a weight basis, based on the acylated polyamine 10 to 25 $> defoliant and / or contain 0 to 150 fo anti-icing agent. Opacifiers are commercially available products, generally highly polar compounds such as oxyalkylenated alkylphenols with or without carboxyl groups. Anti-icing agents are also readily available; however, preference is given to those of the general formula RO ^ H (GH ₃ ) -CH ₂ 07 _m - / CH ₂ CH ₂ p7 _n H ^r , in which R is an alkyl group having 12 to 22 carbon atoms, m and η are integers which Sum m + η is 7 to 30, η has a value from 0 to 4 'and m / n is at least 2. A particularly preferred anti-icing agent is an amine carboxylate salt of the general formula

₀ (CH

R ⁴ -CO-NH (R ¹ )

\ CHR ⁵ CH ₂ O

in which R is a saturated or unsaturated aliphatic hydrocarbon radical having 8 to 24 carbon atoms, R and R are hydrogen atoms or methyl radicals, R is a saturated or unsaturated aliphatic hydrocarbon radical having 11 to 21 carbon atoms, a and b have a value from 1 to 14 and the sum a + b is 2 to 15 (a and b being averages) and the salt contains at least two (CH ₂ CH ₂ O) -G groups. Such an amine carboxylate salt can be easily prepared by neutralizing the corresponding amine containing the oxyalkylene groups with the corresponding hydrocarbon monocarboxylic acid. Since such amine carboxylate salts are not only used as

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anti-icing agents, but also as an anti-corrosion agent and gas cleaning agents work when used in combination with the acylated polyamines are needed lesser amounts of the latter. It has been found that such combinations at relatively low concentrations in gasoline have effects that correspond more closely to the effects of each of the two individual components, if these can be used separately in higher concentrations. So provides a combination of approximately equal parts by weight of the acylated polyamine and the amine carboxylate salt essentially the same carburetor anti-icing protection as about half the amount normally required for this of the amine carboxylate salt on its own, and it achieves essentially the same carburetor cleaning effect as about half the amount of acylated polyamine normally required when used on its own will.

Combinations of acylated polyamine and amine carboxylate salt in weight ratios are suitable for the purposes of the invention from about 1:10 to 10: 1; the preferred ratios range from 1: 1.5 to 1.5: 1. If the combination is in Motor fuels are used, the concentration of the acylated polyamine should be at least 0.002 percent by weight. The preferred acylated polyamine in the combination is that formed from 3 moles of tall oil fatty acid and 1 mole of tetraethylene pentamine will be produced. The preferred amine carboxylate salt in the combination is that consisting of tall oil fatty acid and a straight-chain alkyl or alkenylamine with 18 carbon atoms and about 4 to 6 oxyethylene groups will.

The motor fuel to which the acylated polyamine is added to give it the desirable properties described above A hydrocarbon mixture boiling in the gasoline range is to be lent. The fuel base can be straight chain or

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branched chain paraffins, cycloparaffins, olefins and Aromatics or mixtures of such hydrocarbons "exist, those made from direct distilled gasoline, polymer gasoline, natural gasoline, obtained thermally or catalytically cracked hydrocarbons and catalytically reformed hydrocarbons will. The gasoline can also contain various amounts of conventional Fuel additives, such as anti-knock agents, e.g. tetramethyl lead, tetraethyl lead and mixed lead alkylene, Detergents, dyes, oxidation retardants, anti-icing agents, Anti-rust agents, detergents and agents against pre-ignition contain.

The experiment described below illustrates the preparation of acylated polyalkylene polyamines.

attempt

(a) A reaction flask equipped with a condenser, thermometer, stirrer and additional funnel is charged with 189 g '(1 mol) of tetraethyl enpentamine. Stirring is started and tall oil fatty acid is added through the additional funnel. The tall oil fatty acid has the following composition: 2.3 i ° palmitic acid, palmitoleic 0.6 fo, 2.3 $ stearic acid, oleic acid 41.0 fo, fo 32.8 linoleic acid (cis-9, cis-12), 3.8 # Linoleic acid (cis-9, trans-11), 1.9 $ eicosanoic acid, 4.8 $> linoleic acid (trans-9, trans-11), 2.1 <fo eicosadienoic acid, 2.9 ^ eicosatrienoic acid and 0.9 i ° behenic acid, while the rest consists of unknown components. Although heat develops when the acid is added, additional heat is added to the reaction mixture in order to keep it liquid in the temperature range from 65 to 95.degree. The total amount of tall oil fatty acid added (852 g) corresponds to a carboxylic acid functionality of 3 mol. After the addition of the tall oil fatty acid, a vacuum of 100 mm Hg is applied to the reaction mixture and the reaction mixture is heated to 175.degree. The water vapor that develops during heating is condensed and the condensed water is collected. Stop heating when 52.9 g of water ( $ 98

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theory, based on 1 mole of water per mole of acid converted) have been caught. The acylated tetraethylene pentamine is obtained as a clear, amber-colored liquid, the $ 6.5 Contains nitrogen and has an acid number of 15. The ultrared analysis of the product shows the presence of amide groups and the absence of imidazoline groups.

(b) Following the procedure of part (a), the polyamines listed in Table I are prepared from tall oil fatty acid. the Reaction temperatures are in the range from 125 to 190 ° C and the vacuum in the range from 35 to 100 mm Hg. In all cases the reaction is ended when 1 mole of water per mole reacted Acid has been collected. All condensation reactions are carried out in the absence of a solvent. the Ultrared analysis of the products shows the presence of amide groups and the practical absence of imidazoline groups.

Table I.

attempt Polyamine Moles of tall oil fatty acid No. Diethylenetriamine per mole of polyamine 1 Diethylenetriamine 2. 2 Triethylenetetramine 3 3 Te traäthylenpentamin 2 4th Tetraethylene pentamine . 1 5 2

The following examples illustrate the value of the acylated polyalkylene polyamines as general purpose gasoline additives. _

example 1

The rust protection properties of the acylated polyalkylenepolyamines are determined according to ASTM test standard D-665, method A. In this experiment, 300 ml of fuel are used on hydrocarbons basis, which contains the additive to be examined, stirred with 30 ml of distilled water at 32 ° C, with a

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2406598

cylindrical steel sample is completely immersed in the liquid. The experiment is carried out for 20 hours. When using the fuel base on its own, about 80 ° of the surface of the steel sample is usually covered with rust stains after 20 hours. The tests carried out with the acylated polyamines prepared according to the above test have the following results:

Table II

Connection according to the experiment fo rust a 0 b-1 0 b-2 0 b-3 0 b-4 0 b-5 ' 0 Example2

The value of the acylated polyalkylenepolyamines as a gas cleaning agent is shown by two series of experiments. In the first attempt the effectiveness of the polyamines for examines the removal of deposits already present in the carburetor. The second attempt determines the effectiveness the polyamines for keeping the carburetor clean.

A. In the first attempt, debris is first accumulated in the carburetor under prescribed conditions. The effectiveness of an additive as a carburetor cleaner is then determined by running the engine on a fuel containing the additive and determining the amount of accumulated debris that is removed. This attempt uses Chevrolet six cylinder 3.77 1 engines with Carter No. ₀ 3511-S carburetors fitted with ice towers and heaters ^ an engine is used to get enough throttle body in the shortest amount of time.

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Generate deposits for the cleaning period of the experiment. Since the period of the accumulation of deposits at the The attempt is carried out for about 10 hours during the cleaning period of the experiment takes about 50 hours, the examination can be carried out in a relatively short time, by having one motor for the accumulation of debris and several motors for the cleaning period of the experiment used. In the engine designed for the accumulation of deposits, the annular gap of the top piston ring becomes enlarged by 0.32 cm to 0.35 cm and the ring was inserted in place of the second compression ring so that the top Ring groove remains empty and thereby the amount of gases blown through is increased. The total amount of blown Gas is directed from the dome cover to the carburetor air cleaner. The air cleaner element is removed. The exhaust pipe is modified so that the exhaust gases from the engine are fed to the air purifier of the carburetor. The motor is operated under the following conditions: The manifold vacuum pre-ignition is switched off to provide pre-ignition to maintain 4 ° before top dead center; Motor speed 700-10 rpm; Outlet water temperature 79 - 15 ° C; Air-fuel mixture at maximum vacuum; Carburetor air cooled by passing through an ice tower and then reheating to 32 to 35 ° C; Engine exhaust connected to the air inlet of the carburetor as described. MS-OS, a technical reference fuel, is used as fuel for the "Sequence MS" oil test.

When the engine is started, the valve connecting the exhaust to the engine air inlet is closed, The speed is set at 700 rpm at maximum vacuum. Then the exhaust gas supply valve is opened and the engine speed is maintained at 700 RPM "(the setting of the exhaust gas supply valve is critical). The setting is chosen so that the engine is fed the maximum amount of exhaust gas that it would get when running smoothly Barely tolerates running without stalling. The engine will

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Let it run for 10 hours or so until it stops running under these conditions. Then the carburetor is taken out and assessed by inspection ". A value of 100 means a clean carburetor. If the purity value is higher than 30, an additional build-up of debris is required.

For the cleaning period of the experiment, the dirty carburetor is placed in another engine, which then goes under conditions described above is run, with the exception that normal piston rings are used and the blown gases as well as the exhaust gases are not fed into the air inlet. Before trying new spark plugs are used inserted, the crankcase is loaded with low-detergent SAE 30-01, and the air cleaner housing and the Exhaust systems are cleaned. The cleaning period is 50 hours driven in five sections of 10 hours each, whereby the assessment is made at appropriate intervals to reflect the extent and speed of cleaning determine. The percent cleaning is calculated using the following equation:.

O D Percentage cleaning = —- χ 100

100 - R

In the above equation "Rq is the carburetor value after the deposits have _{accumulated and R Q} is the carburetor value after cleaning. The results are given in Table III.

Table III

Percentage cleaning

Control fuel ■ _: 15

Control fuel + 0.004- fo poly-

amine according to experiment (a) 35

The above results show that the acylated polyamine greatly affects the deposits already present in the carburetor samer way removed.

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B. The second attempt is the Carburetor Cleanliness Test (Onan) carried out in a single-cylinder engine whose test carburetor produced a controlled amount of exhaust gas from a is supplied to another engine in a mixture with air. The air funnel of the experimental gasifier "consists of a two-part Stainless steel bushing that is fitted around the throttle valve rod. The socket looks easy decrease for the purpose of inspection and assessment. The engine periodically idles for 1 minute and partially throttled for 3 minutes, until a total test period of 2 hours is reached. Then the jack is inspected after rated on a scale of values from 0 to 10, in which the value 10 a clean carburetor and the value 0 means a very dirty carburetor. The results are given in Table IV.

Tabel Addition (0.004 f °) IV Onan value None (control fuel) 4.5 Polyamine according to the experiment (a) 8.5 (b-1) 7.4 (b-2) 7.6 (b-5) 6.2 (b-4) 7.4 (b-5) 5.8

The above results show that the acylfien polyamines keep the carburetor clean in an effective manner. A value of at least 7 is for effective cleaning of the carburetor he wishes; it follows that the acylated polyamines according to Examples (b-3) and (b-5) in higher concentrations

tions than 0.004 f ° should be applied.

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Example 3

The value of the acylated polyalkylenepolyamines as anti-icing agents for gasoline is determined in two series of tests. In the first series of tests, the effectiveness of the polyamines Measured for reducing the tendency of hydrous fuels to freeze in cold weather. Of the The second test determines the effectiveness of the polyamines in preventing bisformation on the throttle valve and on the surrounding carburetor wall.

A. The first attempt is initially with water at room temperature saturated gasoline with the additive added, poured into a fuel container and through a closed one Circulating system that includes a cooling coil and a filter cell contains. The pressure drop due to the accumulation of ice across a stainless steel screen (44 μ Mesh size) and the time it takes to complete a To achieve a certain pressure drop, serve as behavior standards for fuels or mixtures of fuel and additive. The results obtained with the acylated polyamine according to experiment (a) are shown in Table V. The test is carried out in the course of 60 minutes or until there is a pressure drop of 355 cm water column has trained.

Table V _/

Pressure drop in the fuel line at -18 ° C

ΔΡ, cm HpO time, min

Control fuel. -355 '15

Control fuel + 0.004 &

Polyamine according to experiment (a) 96.5 60

Δρ ■ = pressure drop.

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B. In the second test, the anti-icing effect of the polyamines on the carburetor is determined using a gasoline containing the additive in question by measuring the number of periods until the engine stalls. The test is carried out with a Chevrolet 3.77 I six-cylinder engine. The area around the gasifier is kept at 4 ° C and a relative humidity of 95 tfo . Under these conditions, cool air, essentially saturated with water, is drawn through the carburetor. The experiment consists in running the engine in a two-part period, namely 20 seconds with the throttle open at a speed of 1600 rpm and 10 seconds at close to closed throttle at a speed of 400 rpm (idle speed). If the test is carried out with a gasoline with poor anti-icing properties, ice will form on the throttle valve and the surrounding carburetor walls, which will bring the engine to a standstill by preventing air flow if the throttle valve is almost closed during the idle period of the test. If you use a gasoline with poor anti-icing properties, the engine will stall in about 3 to 5 periods. The number of periods until the engine stalls is an average of two or more attempts. Generally, an additive is considered effective if it prevents the engine from stalling in about 10 cycles; an excellent anti-icing agent prevents the engine from stalling for at least about 25 periods. /

The compound prepared according to experiment (a) is tested as a carburetor anti-icing agent in a concentration of 0.004 percent by weight in two series of gasoline. Using an unleaded gasoline having a research octane number of 93.3, a Reid vapor pressure of 0.63 kg / cm, a 50 56 distillate point of 103.4 C, and a composition on a volume basis of 58 fo saturated hydrocarbons; 2 $ olefins and 40 $> aromatics, the stall occurs after 6.1 periods (mean). If you add 0.004 weight per

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cent of the polyamines produced after attempting (a) are added, there is no stalling even in 25 periods. When using leaded gasoline with a research octane number of

94 to 96, a Reid vapor pressure of 0.67 kg / cm and a 50 pounds distillate point of 94.4 ° C, the volume basis 55 Ms $ 75 saturated hydrocarbons, 15 "to 20 $ olefins and 20 to 25 $ > Contains aromatics, the engine will stall after 4.5 periods (mean value). If 0.004 percent by weight of the polyamine prepared according to experiment (a) is added to this fuel, the stall will only take place after 7.1 periods (mean value) Polyamine thus shows an excellent anti-icing effect in the gasoline with the higher 50 $ distillate point and a certain anti-icing effect in the gasoline with the lower 50 ^ distillate point. It has been found that this polyamine has an excellent anti-icing effect in a fuel which is poorly responsive to the additive shows when it is used in combination with another anti-icing agent _{, for example an alkyl polyoxyalkylene ether, and in particular C 12-16} H _{25-55 OZCH (CH 3} ) CH ₂ OZ ₇ H

(labeled A in Table VI), where C ₁₀ - ,, - Η «, - * * ■ * a gelid — Io c- \) - JJ

means a mixture of alkyl groups with 12 to 16 carbon atoms, is used. You then get an anti-icing effect, which is higher than the sum of the effects of each anti-icing agent on its own. The results can be found in Table VI. .

T 'abe 1 I ₁ e VI

additive Attempt (a) Weight-i (A) Number of periods
to the point of stalling - • 4.9. None (control fuel) ' Attempt (a) 0.004 6.5 Polyamine according to 0.006 H A. 0.004
0.006 25+ Polyamine according to
+ A

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The results show that the acylated polyamines in fuels, that respond to them, have excellent anti-icing properties in carburetors and in fuels that respond poorly to them in combination with other anti-icing agents also give an excellent anti-icing effect.

Example 4

The value of the acylated polyalkylenepolyamines as cleaning agents for the lower engine compartment is demonstrated by the "MS Sequence VB-Ttest". The "MS Sequence VB Test" is primarily used in industry to evaluate engine oils for their ability to reduce the amount of deposits that form in the engine when operating at low and medium temperatures. However, since it is known that the quality of the gasoline also affects the results, this test is often used to determine the value of a gasoline in reducing engine deposits by keeping the quality of the lubricating oil constant. A Ford Metor with a displacement of 4.74 l is used for this experiment, which runs 192 hours in 48 periods of 4 hours each during the experiment. Each 4 hour period consists of three different modes of operation for the engine, namely idling, running at low temperature and running at medium temperature. Every fourth period is followed by an 8-hour test break. The working conditions are planned in such a way that the formation of sludge and varnish is favored. The fuel used is MS-08, a standard fuel used in the art for the "MS Sequence ^II oil test. The 4-hour period is given in Table VII.

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Time, min lie VII 24 56598 T a b e Speed, rpm step 1 Power, braking horsepower 4-5 Level 2 level 3 Oil temperature, G 500 120 75 Outlet water temperature, C no 2500 2500 Air: fuel ratio 49 86.6 86.6 Vacuum in the suction line, 46 79 96 em ed 9.5 '52 77 Spark pre-ignition 6 ° bdd 15.5 15.5 Blown gases, l / min 43-51 6th 10-16.5 10-16.5 - 26th 26th . - 70-85

voT = before top dead center.

At the end of the experiment, the engine is dismantled and inspected. A group of broad engineering standards is used to obtain numerical values. The total lamb value is obtained by inspecting the rocker arm covers, the intake manifold bottom, the oil filter, the oil pan, the valve area (including the rocker arms), the tappet chamber and the control cover . Each of the seven analyzed areas is assigned a value from 0 to 10 (0 being very dirty and ^10: very acidic group). The sum of the ratings for the seven areas is multiplied by 5/7 to get the overall rating. Therefore, the total sludge value can vary from 0 to 50 (where 50 means very pure). An overall paint value is also obtained by evaluating the following five areas on a scale from 0 to 10 by comparing them with a standardized paint color scale: the piston skirt, the rocker arm cover, the valve tappets, the cylinder wall and the oil pan. The sum of the individual values for these five areas gives the total value. Therefore, the total paint value can also vary from 0 to 50 (where 50 means pure).

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50 98 23/07 09

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The results of the "MS Sequence V-B test" with the according to the experiment (a) polyamines produced are summarized in Table YIII.

Table VIII

Total total additive weight 5 ^ sludge value paint value

None (control fuel). 0 28.7 23.7 polyamine according to experiment (a) 0.004 32.0 26.8

Example 5

This example illustrates the difference in action between acylated polyamines and cyclic imidazoline compounds. Such a cyclic nitrogen compound is prepared by adding 1 mole of tetraethylene pentamine to 3 moles of tall oil fatty acid at 175 ° C in the presence of xylene as a solvent. The condensation is carried out until about 4 moles Water have been split off. After removal of the solvent, the product shows on ultrared spectroscopy a content of imidazoline and amide groups.

A. Table IX shows that the polyamine is effective as a lower engine compartment cleaner while the imidazoline is effective is relatively ineffective. The "MS Sequence V-B" experiments are carried out as described above.

Table IX _

Total total additive weight sludge value paint value

None (control fuel) 0 28.7 23.7 Imidazoline. 0.004 29.1 23.8

Polyamine according to experiment (a) 0.004 32.0 26.8

B. It was also found that only the polyamine, but not the imidazoline, responds to anti-haze additives. One of the additional Properties that are necessary for technically usable gasoline

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Additives are required is that the additives cause emulsification do not favor or interfere with the clean separation between fuel and water. The attempt (United States Federal Water Rating) is according to the ASTM test standard D-1094 carried out, according to which the additive containing Fuel is shaken with an aqueous phosphate buffer solution (pEL 7) and the state of the interface between Fuel. And water are recorded and rated as follows:.

Value ■ · Appearance of the interface

1 "Clear and clean.

1b Small, clear bubbles that are not

cover more than an estimated 50 percent of the interface; no shreds, foam tips and no film at the interface.

2 scraps or foam tips and / or

Film at the interface.

3 loose foam tips and / or

weak foam.

4 dense foam tips and / or

strong foam.

In general, a value of 1b is required for a useful additive. If the additive alone does not give a value of 1b, it is generally customary to add a small amount (0.0002 to 0.0008 percent by weight of the fuel) of an opacifying agent as a further additive in order to bring the fuel-water separation value to 1b or 1 . The opacifiers are highly polar compounds; They include etherified and esterified ethoxylated phenol or amine-formaldehyde condensation products. Table T shows that the polyamine is based on an opacifying agent (which is added to bring the separation value between fuel and water to 1b).

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speaks, while the imidazoline does not respond to it. That

In this case, de-clouding agent is commercially available under the name "Tolad" available.

Tabel

Additive (0.004 wt%) None (control fuel) imidazoline

Polyamine according to experiment (a) imidazoline + de-clouding agent

Polyamine according to experiment (a) + de-clouding agent

Opacifier

none

none

0.0004 f °

0.0004 1 »

¥ ert

4 4 4

1b

Example 6

This example demonstrates the effectiveness of the acylated polyalkylene polyamine in combination with an amine carboxylate salt. The amine carboxylate salt is prepared by reacting equimolar amounts of an oleylamine containing an average of 5 ethylene oxide groups with tall oil fatty acid. Tall oil fatty acid contains 44 $ oleic acid, 52 $> non-conjugated linoleic acid, 8 $> conjugated linoleic acid, 5 $ saturated acids (palmitic acid and stearic acid) and 11 $ other acids. The concentrates given in Table XI are prepared; the amounts given are percentages by weight.

T'a Amines arboxylate bark XI concentrate
C. After experiment (a) herge
made polyamine concentrate
A. concentrate
B. 40 De-clouding agent 80 28.55 Xylene 57.1 4.5 Isopropanol • - 8.6 20th 20th 20th 7.15 14.5

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The concentrates are added to gasoline in various concentrations, and the gasolines are made according to those described above Process examined for anti-icing effect and carburetor cleaning effect. The results can be found in Table XII.

- 25 50 982 3/07 09

I.
ro additive tab 42.8
49.9
46.3 G Amine.
carboxylate hurry XII Drive
fabric R Drive
fabric M Drive
fabric S 11.6
25+
6.0
"8.2
25+ 7.6
25+
25+
Onan value 10.2
25+
25+
25+ OR- Concentration in fuel Number of periods
to the point of stalling 4.5
7.9
7.9
7.7 4.6
7.6
8.0 5.0 '
6.7
8.7
7.9 I.
VJI
cn
V>)
-ρ » ■ g / m ³ 0.0024
0.0048
0.0024 ew .- $ A. Carburetor anti-icing protection 0.0048
0.0024 Polyamine acc.
Attempt (a) None -
Concentrate A 21.4
Concentrate A 42.8
Concentrate B 25.0
Concentrate B, 49.9
Concentrate C 46.3
B. Carburetor cleaning
(Onan cleanliness test) 509823/0 ¹ / No
Concentrate A
Concentrate B
Concentrate C 0.002
0.004
0.002 ο
CD 0.004
0.002

^ Distillate point: fuel R = 94 C; Fuel M = 94 C; Fuel S = 116 ^Ü C.

cn co oo

OR-5634 lh 2A56598

The above results show that the combination gives "a better anti-icing effect from the gas gas than would have been expected from the results of the tests carried out with the individual components. For example, the amine carboxylate salt in fuel R at a concentration of 0.0024 tfo provides anti- icing protection up to 11.6 periods before the engine stops, or an improvement of 7.1 periods over the control fuel, while the compound prepared according to test (a) at a concentration of 0.002 fo has an anti-icing effect up to 6 periods before the engine stalls or a having improved by 1.5 cycles compared to the control of fuel. the combination of 0.0024 i> Aminearboxylat and 0.002 $ in accordance with experiment (a) the compound prepared, however, results in an anti-icing effect of more than 25 periods until the stalling of the engine. In this case, it would be expected been that the combination only has an anti-icing effect of about 1 3.1 periods until the engine stalled.

It can also be seen that the combination has an effect the cleaning or keeping clean of the gasifier, which is almost as great as the effect of the connection according to the experiment (a).

With the concentrates B and G at concentrations of 42.8 g / m ⁵ and 46.3 g / m ⁵ in Chevrolet six-cylinder vehicles under programmed chassis dynamometer period tests according to the Automotive Manufacturers Association (AMA) Tests carried out have confirmed the cleaning effect of the compound produced according to * Test (a) and of the combination corresponding to concentrate 0.

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Claims (10)

Claims Engines ζ with good anti-icing and rust protection properties as well as cleaning action for the carburetor and the lower engine compartment on the basis of one in the gasoline area boiling hydrocarbon mixture, characterized in that it is a generally liquid, acylated Polyalkylenepolyamine, which is practically free of nitrogenous cyclic groups and the general formula EAR has, wherein R is hydrogen and / or a radical R'-C- and R 'is a saturated or unsaturated aliphatic hydrocarbon radical with 9 "to 21 carbon atoms", while η has the value 2 or 3 and χ has a value from 2 "to 6, in amounts from 0.002 to 0.02 percent by weight, based on the hydrocarbon mixture contains. 2. Gasoline additive, the hydrocarbon mixtures of the gasoline boiling range a good anti-icing and rust protection effect as well as cleaning effect for the carburetor and the gives lower engine compartment, characterized in that it consists of a 30 to 70 percent by weight solution In general, there is liquid, acylated polyalkylenepolyamine, which is practically free of nitrogenous cyclic groups is and the general formula EAR - 28 - 509823/0709 OR-5634 <jft O • A / « ^% η in which R is hydrogen and / or a radical R'-C and R ^{1 is} a saturated or unsaturated aliphatic hydrocarbon radical having 9 "to 21 carbon atoms, while η is 2 or 3 and χ is 2 Ms 6. 3. Gasoline additive according to claim 2, characterized in that it contains an opacifier in amounts of 10 "to 25 percent by weight, "based on the polyamine. 4-. Petrol additive according to claim 2, characterized in that he an anti-icing agent in amounts of 0 "to 150 percent by weight, based on the polyamine. Petrol additive according to Claim 4, characterized in that the anti-icing agent has the general formula _0. (CHR ² CH ₂ 0) _a H R ⁴ _C-0-NH (R ¹ > (CHR ³ CH ₂ 0) _b H. ι
has, in which R is a saturated or unsaturated one aliphatic hydrocarbon radical with 8 "to 24 carbon 2 3
atoms, R and R independently of one another are hydrogen or methyl radicals and R is a saturated or unsaturated aliphatic hydrocarbon radical with 11 to 21 carbon atoms, while a and b have values from 1 to 14 and the sum a + b has a value from 2 to 15 ( where a and b are mean values), the salt containing at least two (CH ₂ CH ₂ O) groups. 6. gasoline additive according to claim 5, characterized in that the weight ratio of polyamine to anti-icing agent ranges from 1: 1.5 to 1.5: 1. 7. gasoline additive according to claim 6, characterized in that the amine carboxylate salt is a salt of tall oil fatty acid with a straight-chain alkyl or alkenylamine with 18 carbons -29. '* 50 9823/07 09 OE-5634, _ft 2 * 56598 material atoms and 4 "to 6 oxyethylene groups. 8. gasoline additive according to claim 2 »characterized in that E'-C- denotes the acyl radical of tall oil fatty acid, η denotes Value 2 and χ has the value 4. 9. gasoline additive according to claim 2, characterized in that η the fourth 2 and χ has a value of 2 to 4. 10. Motor gasoline according to claim 1, characterized in that η has the value 2 and χ has a value of 2 to 4. - 30 50982 3/0709