DE1248643B - Process for the preparation of oil-soluble aylated amines - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C 07 c

13 ψ

German class: 12 ο - 21

Number: 1 248 643

File number: L 35070IV b / 12

Filing date: January 7, 1960

Opened on August 31, 1967

The invention relates to a process for the preparation of oil-soluble acylated amines, which thereby is characterized in that a substituted succinic acid of the general formula

CHCOOH
CH ₃ COOH
or their anhydride of the general formula

R.
CH-CO.

CH ₉ CO

in which R an aliphatic derived from a polyolefin or one derived from a copolymer Styrene and an olefin which is more than 90% olefin units contains, derived hydrocarbon radical having at least 50 carbon atoms, with at least half the equivalent amount, preferably with the equivalent amount of an ethylene amine general formula

H ₂ N- / CH ₂ -CH-NHX-H

in which χ is an integer and R _{1 is} a low molecular weight alkyl radical or a hydrogen atom, or technical mixtures thereof are ^{condensed at temperatures from 80 to 200 °} C. with removal of the water formed during the reaction.

The acylated amines prepared according to the invention are particularly suitable as additives for lubricants, which are used in the engine housing of internal combustion engines.

In the engine housing of internal combustion engines, there is inevitable contamination of the lubricant through foreign bodies, such as impurities, coal particles, water and decomposition products of the oil itself, a.

The most important of these impurities is true-

Process for the preparation of oil-soluble
acylated amines

Applicant:

The Lubrizol Corporation,

Cleveland, Ohio (V. St. A.)

Representative:

Dr. E. Jung and Dr. V. Vossius, patent attorneys,

Munich 23, Siegesstr. 26th

Named as inventor:

William M. LeSuer, Cleveland, Ohio;

George R. Norman, Lyndhurst, Ohio (V. St. A.)

Claimed priority:

V. St. v. America March 30, 1959 (802 667)

Apparently the water, which is obviously responsible for a thick sludge settles. In the absence of water, the solids of this sludge would likely be circulate with the oil and eliminated by the oil filter. So by settling this sludge, that becomes Affects engine operation; it is therefore desirable to prevent the sludge from settling. The presence of water and the formation of sludge in a lubricating oil depend largely on the operating temperature of the oil. At high operating temperatures, the water evaporates as soon as it accumulates. The other foreign matter ^ are then removed by the filter. At low oil temperatures however, water collects and allows sludge to form. The conditions faced by a lubricant exposed in the engine housing also largely determine the performance of this lubricant.

High working temperatures occur in an engine that is running at a relatively constant high speed running around. In this case there is an accumulation of water and with it the formation and settling of Mud very unlikely. In contrast, when a motor vehicle is used for short journeys, the lubricant is alternately hot and cold in the motor housing,

709 639/564

whereby the accumulation of water is favored. In this case, the sludge build-up is serious Problem also caused by the addition of known cleaning agents such as metal phenates and sulfonates of alkaline earth metals, could not be solved satisfactorily. Although these well-known cleaning agents, e.g. salts of a polyvalent metal of a monoamide of 2,5-endo-ethylene- / 13,4-cyclohexene-1,6-dicarboxylic acid or the condensation product of such an amide with an alkanethiol, sludge formation in motor oils at high operating temperatures prevent satisfactory is their effect at low operating temperatures or when the lubricant in the motor housing is alternately hot and cold, considerably less.

Amides of succinic acids or succinic anhydrides substituted by alkyl or alkenyl groups, but whose alkyl or alkenyl groups contain at most 12 or 15 carbon atoms (cf. U.S. Patents 2,604,451, 2,588,412 and 2 540 800). However, these corrosion protection agents do not act as dispersing agents whose substituents are too small.
^The use of amides of aliphatic daliphatic carboxylic acids with 6 to 24 ffatomen and hydroxyl derivatives of aliphatic amines did not lead to the desired result (cf. British patent specification 681 554).

The difficulties mentioned are solved by the fact that the mineral lubricating oils after Acylated amines prepared by the method of the invention in amounts of about 0.1 to 5 weight percent as Adding dispersant.

The oil-soluble acylated amines prepared by the process of the invention can be prepared from simple

acyclic diamides, cyclic diamides, polymers Amides or mixtures of these amides exist. Furthermore, by further implementation of amide groups imide groups are also formed. You can also add amino acid salts to this mixture to be available.

The size of the substituent of the succinic acid used as the starting material for the process of the invention or their anhydride is of particular importance. It is namely important that this substituent contains at least 50 carbon atoms. The starting materials for these aliphatic hydrocarbon substituents are polyolefins, for example polyethylene, polypropylene and preferably polyisobutylene. The condensation of a polyisobutylene with a molecular weight of 750 with maleic anhydride results in an alkenylsuccinic anhydride, which in the further reaction with an ethylene amine the following general

ao formula a particularly effective lubricating oil dispersant represents. Polyisobutylenes of this particular molecular weight are commercially available and based on Particularly suitable for the process of the invention because of the effectiveness of the substances produced therefrom.

The substituent can also come from a copolymer of unsubstituted or substituted one Derive styrene and isobutylene or other aliphatic olefins that contain more than 90% olefin units contains.

The substituted succinic acids and anhydrides thereof, amines are acylated with the aid of which are novel compounds, which can be prepared by heating maleic anhydride with a high molecular weight olefin or chlorinated high molecular weight olefin to about 150 to 200 ⁰ C, as illustrated by the following structural formulas :

CHCO

R - CH = CH ₂ +

CHCO

R-CH = CHCHCO

CH ₂ CO

CHCO

R-CH ₂ CH ₂ Cl +

CHCO

R-CH- = CHCHCO

CH ₂ CO

: o 4 HCi

However, it is not certain whether the implementation will proceed exactly according to this formula, especially with regard to it to the carbon atom of the high molecular olefin or chlorinated high molecular olefin, the is reacted with the maleic acid or its anhydride.

Substituted succinic anhydrides and their derivatives have been known for some time (cf. the USA. Patent 2 133 734). It is also known that these compounds because of their rust and corrosion preventive properties Properties and their viscosity-temperature behavior as lubricant additives are suitable (see US Pat. No. 2,334,158). Such additives, however, have no dispersing effect on. In contrast to this, the acylated amines which can be prepared according to the invention are suitable due to the large chain length of the substituent R in the substituted succinic acid or its anhydride very good as a dispersant in lubricating oils.

The substituted succinic anhydride is reacted immediately with the ethylene amine or beforehand converted into the acid.

"Ethylenamine" includes compounds of the general formula

H ₂ N- (CH ₂ CHNH) ^ H

to be understood in which χ is an integer and R _{1 is} a low molecular weight alkyl radical or a hydrogen atom, for example ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine. These compounds are described in detail in the "Ethylene Amines" section in Kirk-Othmer, "Encyclopedia of Chemical Technology", Vol. 5, 1950, pp. 898-905.

These substances are most useful through implementation made of ethylene dichloride with ammonia, mixtures of ethylene amines including cyclic condensation products such as piperazines can be obtained. Also from pure ethylenedi- The acylated amines can be prepared or polyamines. One because of its light weight and cheap accessibility and its dispersing properties is particularly suitable acylated amine made from a mixture of made by reacting ethylene chloride and ammonia Ethylenamines, the composition of which corresponds to that of tetraethylene pentamine. This fabric is under the Trade name "Polyamine H" available.

As already noted, at least half of it must be

equivalent amount of di- or polyamine used per equivalent of the substituted succinic anhydride so that the acylated amines have satisfactory dispersion properties. Preferably sets the starting materials in equivalent amounts.

The chemical "equivalence" of ethylene amine refers to the nitrogen content; i.e., an amine with

4 nitrogen atoms per molecule contains 4 equivalents

to per mole.

The implementation takes place with elimination of water, which is removed during formation. After salt formation, the first stage is likely to be formation of a hemiamide:

R - CHCO
CH ₂ CO

H ₂ NR ₁ R - CHCOOH

CH ₂ CONHR ₁

followed by salt formation:

R - CHCOOH R - CHCOOeH ₃ N ⁹³ R ₁

+ H ₂ NR ₁ ---> CH _{2 CONHR 1} CH ₂ CONHR ₁

and finally the dehydration of this salt to form the acylated amine:

R - CHCOOH ₃ N ^ ₁
CH ₂ CONHR ₁

R - CHCONHR ₁

CH ₂ CONHR ₁

As already mentioned, imides are also formed.

The first two stages appear to be self-paced when mixing, while the third stage requires heating. Temperatures in the range of about 80 suffice to 200 ⁰ C and temperatures zwisehen about 100 and 16O ⁰ C are preferable. To remove the water, toluene in particular is added as an entrainer and the water is distilled off azeotropically.

The examples illustrate the invention.

example 1

A polyisobutenyl succinic anhydride was prepared by reaction of a chlorinated polyisobutylene with maleic anhydride at 200 ⁰ C. The polyisobutenyl radical had a molecular weight of 850 and the alkenylsuccinic anhydride formed had an acid number of 113 (corresponding to an equivalent weight of 500).

To a mixture of 500 g (1 gram equivalent) of this polyisobutenyl succinic anhydride and 160 g Toluene was added 35 g (1.02 gram equivalents) of diethylenetriamine at room temperature.

The addition took place in portions over the course of 15 minutes, and an initial exothermic reaction caused the temperature to rise to 50 ^° C. The mixture was then heated and an azeotropic mixture of water and toluene was distilled off from the mixture. After no more water was distilled off, the mixture was ^{heated to 150 °} C. at 20 torr in order to remove the toluene. The residue was diluted with 350 g of mineral oil. The nitrogen content of this solution was 1.6%

Example 2

Example 1 was repeated using 31 g (1 gram equivalent) of ethylene diamine. The nitrogen content of the solution of the final product in mineral oil was 1.4 ° / _0th

Example 3

Example 1 was repeated using 55.5 g (1.5 gram equivalents) of an ethylene amine mixture, the composition of which corresponded to that of triethylenetetramine. The nitrogen content of the solution of the final product was 1.9 ° / _0th

Example 4

Example 1 was repeated using 55.0 g (1.5 gram equivalents) of triethylenetetramine. The nitrogen content of the final product solution was 2.2%.

Example 5

A mixture of 140 grams of toluene and 400 grams (0.78 gram equivalents) of a polyisobutenyl succinic anhydride (with an acid number of 109, made from maleic anhydride and the chlorinated Polyisobutylene according to Example 1) was 63.6 g (1.55 gram equivalents) at room temperature Ethylenamine mixture added, the average composition of which is tetraethylene pentamine and which is known under the trade name "Polyamine H". The mixture was heated around the azeotropic mixture of water and toluene

distill and then heated at 20 Torr to remove the toluene to 150 ⁰ C. The remaining polyamide had a nitrogen content of 4.7%.

Example 6

Example 1 was repeated using 46 grams (1.5 gram equivalents) of ethylene diamine. the Solution of the final product had a nitrogen content of 1.5%.

Example 7

A polyisobutenylsuccinic anhydride with an acid number of 105 and an equivalent weight of 540 was prepared by reacting a chlorinated polyisobutylene (with an average molecular weight of 1050 and a chlorine content of 4.3%) and maleic anhydride. A mixture of 300 parts by weight of the polyisobutenylsuccinic anhydride and 160 parts by weight of mineral oil was admixed with an equivalent amount (25 parts by weight) of “polyamine H” (cf. Example 5) ^{at 65 to 95 ° C.} The mixture was then heated to 15O ⁰ C, to drive out everything in the reaction water formed. In order to remove even the last traces of water, nitrogen was blown through the mixture at this temperature. The residue was diluted with 79 parts by weight of mineral oil and this oil solution had a nitrogen content of 1.6%.

Example 8

A mixture of 2112 g (3.9 gram-equivalents) of the polyisobutenyl succinic anhydride of Example 7, 136 g (3.9 gram-equivalents) of diethylene triamine and 1060 g of mineral oil was heated for 1 hour at 140 to 150 ⁰ C. Nitrogen was bubbled through the mixture at this temperature for an additional 4 hours to remove the water. The residue was diluted with 420 g of mineral oil and this oil solution had a nitrogen content of 1.3%.

Example 9

To a solution of 1000 g (1.87 gram-equivalents) of the polyisobutenyl succinic anhydride of Example 7 in 500 g of mineral oil ⁰ C was added 70 g (1.87 gram equivalents) of tetraethylene pentamine are added at 85 to 95 wt. The mixture was then heated to 150-165 ° C for 4 hours while sparging with nitrogen to remove the water. The residue was diluted with 200 g of mineral oil and this oil solution had a nitrogen content of 1.4%.

Example 10

A polypropenylsuccinic was prepared by reacting a chlorinated polypropylene (having a molecular weight of about 900 and a chlorine content of 4%) with maleic anhydride at 200 ⁰ C. The product has an acid number of 75. To a mixture of 390 g (0.52 gram equivalents) of this polypropenylsuccinic anhydride, 500 g of toluene and 170 g of mineral oil, 22 g (0.52 gram equivalents) of "Polyamine H" (see Example 5) were added in portions. given. The reaction mixture was refluxed for 3 hours and the water was removed azeotropically with toluene; the remaining toluene was then ^{removed by heating to 150 °} C. at 20 torr. The residue contained 1.3% nitrogen.
5

Example 11

A substituted succinic anhydride was made by reacting maleic anhydride with a

ίο chlorinated copolymer made from isobutylene and styrene. The copolymer consisted of 94 parts by weight of isobutylene units and 6 parts by weight of styrene units, had an average molecular weight of 1200 and was chlorinated up to a chlorine content of 2.8 percent by weight. The substituted succinic anhydride formed had an acid number of 40.710 g (0.51 gram equivalents) of this substituted succinic anhydride and 500 g of toluene were added in portions with 22 g (0.51 gram equivalents) of "polyamines Η". The mixture was heated for 3 hours at reflux temperature, to remove any water by azeotropic distillation to remove, and then at 150 ⁰ C and 20 Torr, the toluene. The residue contained 1.1 percent by weight nitrogen.

Example 12

A substituted succinic anhydride was made by reacting maleic anhydride with a chlorinated copolymer made from isobutylene and isoprene. The copolymer consisted of 99 parts by weight of isobutylene units and 1 part by weight of isoprene units; its molecular weight was 28,000, and the chlorine content of the chlorinated copolymer was 1.95%.

This alkenylsuccinic anhydride had an acid number of 54. A mixture of 228 g (0.22 gram equivalents) of an oil solution of this alkenylsuccinic anhydride, 58 g of additional mineral oil, 500 g of toluene and 9.3 g (0.22 gram equivalents) of “polyamines Η” (cf. Example 5) was ^{heated to 110 to 120 °} C. for 3 hours, the water being removed azeotropically with toluene. After the water had been removed, the toluene was distilled off at 150 ° C. and 20 torr. The residue had a nitrogen content of 1.1%.

Example 13

A polyisobutenyl succinic anhydride was prepared by reacting a chlorinated polyisobutylene with maleic anhydride. The chlorine content of the chlorinated polyisobutylene was 2% and the average molecular weight 11,000. The polyisobutenylsuccinic anhydride had an acid number of 48. A mixture of 410 g (0.35 gram equivalents) of this anhydride, 15 g (0.35 gram equivalents) "polyamines Η" (cf. Example 5) and 500 g of toluene was refluxed for 4 hours to azeotropically remove the water with toluene. The toluene was then ^{removed at 150 °} C. and 20 torr. The nitrogen content of the residue was 1.3%.

Example 14

Example 5 was repeated, but with 0.94 gram equivalents of "polyamines Η" instead of

1.55 gram equivalents. The nitrogen content of the product was 3%.

Example 15

A polyisobutenyl-substituted succinic acid was prepared by hydrolyzing the corresponding anhydride (the anhydride itself was obtained by condensing a chlorinated polyisobutylene and maleic anhydride). To 1152 g (1.5 gram equivalents) of a 70% mineral oil solution of this polyisobutenylsuccinic acid with the acid number 62 was added 59.5 g (1.5 gram equivalents) of "Polyamine H" at room temperature. The mixture was heated to 150-167 ° C for 7 hours; during this time a total of 19.5 g of water was distilled off. The residue was mixed with 174 g of mineral oil and filtered at 150 ⁰ C. The filtrate contained 1.6 ° / ₀ nitrogen.

Example 16

A mixture of 1056 g (2.0 gram equivalents) of the polyisobutenylsuccinic anhydride according to the previous example (in which the polyisobutenyl group has a molecular weight of 850), 89 g (2.0 gram equivalents) of di- (1,2-propylene) triamine (with a nitrogen content of 31.3% X 370 g of mineral oil and 100 g of toluene was heated for 5 hours at reflux temperature (180 to 190 ⁰ C). a total of 18 g of water was distilled off azeotropically with toluene. The residue was taken at 20 torr at 150 ° C in order to completely remove even the last traces of water.The nitrogen content of the residue was 1.9 _% .

Example 17

A polyisobutylene with an average molecular weight of 50,000 was chlorinated to a chlorine content of 10 percent by weight. This chlorinated polyisobutylene was reacted with maleic anhydride to form the corresponding polyisobutenylsuccinic anhydride with an acid number of 24. 6000 g (2.55 gram-equivalents) of this anhydride was admixed in the course of 45 minutes in portions with 108 g (2.55 gram-equivalents) "Polyamine H" at 70 and 105 ⁰ C. The resulting mixture was for 4 hours at 160 to 180 ° C and nitrogen was bubbled through to drive off the water. After the water had been completely removed, the product was filtered. The filtrate contained 0.6 ° / ₀ nitrogen.

Comparative experiment A

An alkenyl succinic anhydride having an alkenyl group with fewer than 50 carbon atoms (27 carbon atoms) was prepared from a polyisobutylene with an average molecular weight of 375. This polymer was chlorinated to a chlorine content of 9.7% and then reacted with maleic anhydride. The resulting polyisobutenylsuccinic anhydride with an acid number of 190 had an equivalent weight of 300. Following the procedure of Example 1, 1.0 gram equivalent of this polyisobutenylsuccinic anhydride was reacted with 1.0 gram equivalent of "polyamine H" (see Example 5). Mineral oil was added to the end product and a 58% solution was made. The nitrogen content was 3.2 ⁰ I ₀ .

Comparative experiment B

Another alkenyl succinic anhydride with one containing fewer than 50 carbon atoms (12 C atoms) Alkenyl group was obtained by alkylation of

ίο Maleic anhydride made with tetrapropylene. Equivalent amounts of this tetrapropylene succinic anhydride and triethylenetetramine in toluene were heated to reflux until all of the water was removed. The toluene was then removed by heating to 155 ⁰ C at 20 torr and the residue dissolved in mineral oil to a 60 ° / ₀ solution. This oil solution had a nitrogen content of 4.8 ⁰ I ₀ .

Comparative experiment C

About 227 parts by weight (1 mole) of technical grade triamylamine was added in small proportions to about 266 parts by weight (1 mole) of a commercial mixture of alkenyl succinic anhydrides having C _{10 to} C ₁₂ alkyl substituents. Heat was evolved during the addition of the amine and the mixture was held at about 120 ° C for about 5 minutes.

Comparative experiment D

A commercially available mixture of alkyl succinic anhydrides of the type used in Comparative Experiment C and octadecylamine were reacted in a molar ratio of 2: 1. 14.5 g of anhydride and 5.0 g of amine were stirred together in a beaker, the heat of reaction increasing the temperature to about 80.degree. The mixture was then heated ^{to 105 to HO 0 C for about 1 hour.}

Comparative experiment E

52.6 g (0.5 mole) of the amine of the formula
(HIGH ₂ ) ₃ C-NH ₂

and 141.2 g (0.5 mole) oleic acid were in the presence of toluene for 4 hours at 160 ⁰ C in a 1-1 flask, which, thermometer, nitrogen inlet tube, reflux condenser and water separator was equipped with a stirrer, heated under reflux. There were about 16 cm ³ (0.89 moles) of water collected. The toluene was then ^{removed by heating to 160 °} C. under a pressure of 30 torr, an oily, amber-colored, liquid product of indeterminate structure remaining.

The acylated amines prepared by the process of the invention are used as dispersants in mineral lubricating oils used. They are miscible with these lubricating oils in all proportions and become common added in amounts of about 0.1 to 5 percent by weight of the lubricating oil. The optimal concentration usually depends on the type of mineral oil as well as the conditions under which the oil is used and are within a narrower range of about 0.5 to 3 weight percent.

As already mentioned, the acylated amines produced by the process of the invention effect a remarkable improvement in the dispersing properties of mineral lubricating oils. Most

709 639/564

However, common lubricants are used under very different conditions, and it is therefore it is necessary to add more than one additive in order to achieve a satisfactory effect. Although the acylated amines prepared by the process of the invention are used as dispersants It is very effective at low temperatures and significantly improves the dispersing properties but often necessary to use these dispersants together with other additives, e.g. B. with Metal dispersants, corrosion and oxidation inhibitors, extreme pressure agents, viscosity improvers, Lowering pour point, anti-foaming agents.

A particularly favorable combination of additives for lubricating oils in motor housings is the combination of the acylated amines of the invention with a metal dispersant. Such metal dispersants are for example the alkaline earth sulfates, alkaline earth No added salts of carboxylic acids and alkaline earth phenolates. Particularly The alkaline earth sulfonates are valuable in this combination, especially the neutral and basic ones alkyl aromatic barium sulfonates, calcium mahogany sulfonates, and the alkyl aromatic calcium sulfonates. The term "basic sulfonates" means here that the compounds have a stoichiometric excess of metal, usually as metal carbonate, to the sulfonate anion of the compound.

Another valuable combination is that of the acylated amines of the invention with an anti-corrosive agent. Such anti-corrosion agents are metal phosphorodithionates, various olefin-phosphorus sulfide reaction products and phenolic compounds. A particularly effective metal _{phosphorodithionate is zinc dialkyl phosphorodithionate having the C 3} to C ₆ alkyl groups, and a similarly effective olefin-phosphorus sulfide reaction product is a turpentine-phosphorus pentasulfide condensate.

The advantages of the acylated amines prepared according to the process of the invention emerge from the results of a series of tests with mineral lubricating oils for engine housings which were used in rental cars which were each driven over 80,000 km. Ten six-cylinder Chevrolet cars, built in 1958 (without oil filter), were used in this experiment. In all cases, the lubricating oil in the engine housing was a sulfur-free "mid-continent petroleum oil" with a viscosity of 39.7 cSt at 38 ⁰ C and a viscosity index of 112, which is 5.9 percent by volume of a polyalkyl methacrylate to improve the viscosity index and 0. 59 percent by volume of a zinc dialkyl phosphorodithionate (with isobutyl and a mixture of primary amyl groups).

Samples of the crankcase oil were taken at each oil change after approximately 4,800 km of operation and these samples were mixed. 30 cm ^{3 of} these mixed samples were mixed with 1 percent by weight of the dispersant to be examined and 2 percent by weight of water. The mixture was then homogenized with a high-speed stirrer for 5 minutes, ^{poured into a graduated 100 cm 3} centrifuge glass which tapered to a point and centrifuged for 2 hours at 1500 rpm. The various dispersants were assessed according to the volume of the deposited substances in cubic centimeters and according to the cloudiness of the oil layer above.

Accordingly, the more effective dispersants will produce the smallest deposits at a proportionate rate increased cloudiness of the oil layer.

The clarity of the oil layer was determined by the amount of light emitted by a 3 volt, 0.75 watt incandescent lamp was sent out and passed through this layer.

The test results are shown in Table 1.

Table 1

Investigated addition
(1 percent by weight)
without solvent)

Known dispersant
according to comparative experiment A.

Dispersant after

Example 5

Dispersant after

Example 3

Dispersant after

example 1

Dispersant after

Example 2

Dispersant after

Example 6

Deposits of
Drain oil

cm

AbIa-! Cloudiness of the yeast oil layer

0.3 I clearly translucent

0.3! clear translucent

0.0 'impermeable

0.0 impermeable

0.1 1 impermeable

0.1; severely clouded

0.0 heavily clouded

The dispersing properties of the acylated amines prepared by the process of the invention can also be illustrated by the results of an oxidation-dispersing experiment. In this experiment, a 350 cm ³ sample of a lubricating oil containing the dispersant is placed in a large borosilicate tube 381 mm long and 50.8 mm in diameter. A 34.9 χ 149.2 mm steel plate is immersed in the oil. The sample is then heated for 48 hours 148.9 ⁰ C with air at a rate of 101 / hr. is blown through the oil. The oxidized sample is cooled to 48.8 ⁰ C, homogenized with a high-speed agitator for 5 minutes allowed to stand for 24 hours at room temperature and finally filtered at 20 Torr through two layers of Whatman filter paper no. 1,. The weight of the precipitate after washing with petroleum and drying serves as a measure of the effectiveness of the additive, ie the greater the weight of the precipitate, the smaller the dispersing effect.

Two changes to this procedure are possible; both make the experiment stricter; the one part of the experiment 48 hours to 96 hours may be extended, and on the other hand, may comprise from 0.5 ° / ₀ of water, based on the weight of the sample, the oxidized oil are added before homogenization.

The oil used in this experiment (Table 1) was a normal refined "Mid-Continent petroleum oil" having a viscosity of about 43 cSt at 38 ⁰ C and a Eisennaphthenatgehalt of 0.001 weight percent (to promote oxidation).

Table 2

Results of the oxidative Investigated addition Dispersing (1.5 percent by weight Attempt without thinner) (mg deposit) Trial amount 100 ml of oil No addition ... 144 No addition 275 (b) No addition 1000 (a) (b) Known dispersant after Comparative experiment A 738 Known dispersant after Comparative experiment B 1060 (b) Known dispersant after Comparative experiment C 845 (b) Known dispersant after Comparative experiment D 496 (b) Known dispersant after Comparative experiment E 642 (b) Dispersant according to Example 1 .... 0.7 (b) Dispersant according to Example 2 .... 0.7 (b) Dispersant according to Example 3 .... 1.0 (b) Dispersant according to Example 4 ... 1.2 (b) Dispersant according to Example 5 ... 1.5 (b) Dispersant according to Example 6 .... 0.7 (b) Dispersant according to Example 9 .... 0.5 (b) Dispersant according to Example 10 ... 3.2 (b) Dispersant according to Example 11 ... 10.2 (b) Dispersant according to Example 12 ... 19.5 (b) Dispersant according to Example 13 ... 2.7 (b) Dispersant according to Example 14 ... 0.3 Dispersant according to Example 14 ... 1.2 (b) Dispersant according to Example 14 ... l, 7 (a) (b) Dispersant according to Example 15 ... 1.3 (b) Dispersant according to Example 16 ... 0.9 (b)

Change (a): 96 hour attempt.

Change (b): 0.5% water was used in the experiment.

The test results clearly show the superiority of those produced by the process of the invention Dispersants.

Further examples of the effect of the dispersants prepared by the process of the invention in engine oils were modified by a modification of the CRC-EX-3 engine test (the test usually lasts 96 hours). This attempt is in a publication »Deposition in Stop- and Go-Type Service, Comparison of EX-3 and Field Test Results, Appendix C, Coordinating Research Council, November 25, 1952 «. This attempt

ίο is used to assess for under light conditions working lubricants. Here, the lubricant is in the engine housing of a six-cylinder "Chevrolet Powerglide engine", Built in 1954, 144 hours used under cyclically repeating conditions, where each cycle is composed as follows:

2 hours at an engine speed of 500 + 25 U / min under no load at an oil sump temperature of 37.8 to 51.7 ⁰ C, ratio of air to fuel 10: 1;

then 2 hours at an engine speed of 2500 i 25 rpm under a load of 40 brake horsepower at an oil sump temperature of 71.1 to 76.7 ° C., ratio of air to fuel 16: 1; finally 2 hours at an engine speed of 2500 i 25 rpm under a load of 40 brake horsepower at an oil sump temperature of 115.6 to 121.1 ° C, ratio of air to fuel ^{16: 1}

After completing the experiment, the engine is disassembled and the individual parts are examined for deposits. The dispersant in the motor oil is then made according to the following criteria judged:

1. Filling the piston rings,

2. Amount of sludge in the engine (scale 80 to 0, with 80 no sludge and 0 very strong sludge formation means) and

3. Total amount of deposits, d. H. Mud and paint, in the engine (scale 100 to 0, where 100 means no deposits and 0 means very heavy deposits).

The results are summarized in Table 3.

Tabel

Approved lubricant Piston ring filling
Vo Muddy
in the engine
7o total
deposits
0 /
/ 0 1. Lubricating oil + 2.33 percent by weight of the dispersant
by means of example 7
2. Lubricating oil + 2.33 percent by weight of the dispersant
by means of example 8 1
0 76.9
73.3 95.7
91.3

Claims (1)

Claim: Process for the preparation of oil-soluble acylated amines, characterized in that that you have a substituted succinic acid of the general formula CHCOOH CH ₂ COOH or their anhydride of the general formula
R. CH-CO, CH ₂ CO in which R is an aliphatic derived from a polyolefin or a copolymer of styrene and an olefin which is more than 90 ° / ₀ Contains olefin units, derived hydrocarbon radical with at least 50 carbon atoms, with at least half the equivalent amount, preferably with the equivalent amount of an ethylene amine of the general formula H ₂ N - / CH ₂ -CH - NH \ - H in which .v is an integer and R _{1 is} a low molecular weight alkyl radical or a hydrogen atom, or technical mixtures thereof Temperatures of 80 to 200 ⁰ C condensed with removal of the water formed during the reaction. Considered publications: British Patent No. 681,554; U.S. Patents Nos. 2,133,734, 2,182,178, 334,158, 2,540,800, 2,588,412, 2,604,451, 2,654,708, 654 709; Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Vol. 8, 1952, pp. 656 to 658; Vol. 11, part 2, 1958, p. 4, 16/17. A priority document was displayed at the time of the announcement.