DE1594553A1 - Amide-amidine derivatives of polyalkenylsuccinic acid as additives for lubricating oils and fuels - Google Patents

Description

"Dr.WaHer hatchet

Dr / !. <■ '■ ^; . ■ '·· ■ - vol

Frankiui t a. M.-Höchst Adeionstrasse 58 ♦ TeL 312ό 49

..1966

Our ITo. 13 287

Rohm and Haas Company Philadelphia, Pi., V.St.A.

Amia-amiaine derivatives of polyalkenyl succinic acid as an additive for lubricating oils and fuels

According to the present invention, new amide-amidine derivatives are to be Polyalkenylsuccinic acid, which is made up by appropriate implementation Polyalkeny! Succinic anhydride are obtained as additives for Lubricating oils and fuels are used, taking under fuel en understood both motor fuels and heating oils will.

The compounds used according to the invention correspond to the formula

r /

(D

909839/124 *

In this formula:

R is an alkenyl radical with about 30 to 200 carbon atoms
(this means that this residue has a molecular weight of
about 400 to 3000, preferably about 600 to 2500);

R _{1 is} an alkyl radical having 1 to 24 carbon atoms or one

Phenyl, naphthyl, benzyl or alkyl-substituted phenyl, ITaphthyl or benzyl radical, in the latter cases
The alkyl substituents have a total of up to 24 carbon atoms
may contain;

R _{2 is} hydrogen or an alkyl radical having 1 to 24 carbon atoms;

R ₁ + R ₂ can, together with the nitrogen atom to which they are attached, also form a morpholine, thiamorpholine, piperidine
or form pyrrolidine ring;

R _{5 is} hydrogen, 2-hydroxyethyl, 2-aminoethyl, 2- or 3-hydroxypropyl, 2- or 3-aminopropyl, 2- or 3- (2-aminoethyl / aminopropyl;

D is a divalent saturated chain of 2 to 3 carbon atoms whose valences are available through hydrogen atoms or
Alkyl groups with a total of 12 carbon atoms or combinations of hydrogen atoms and alkyl groups with a total of
12 carbon atoms or a 1,2-cyclohexylene radical are saturated.

Typical substituents are, for example:

in the case of R ₁ : methyl, butyl, octyl, dodecyl, octadecyl,

Tetracosyl, phenyl, haphthyl, benzyl, butylphenyl, oetylphenyl, dodecylphenyl, di οcty I-phenyl, butylnaphthyl, butylbenzyl or
Octylbenzyl;

in the case of R ₂ : hydrogen, methyl, butyl, O _c tyl, dodecyl,

Octadecyl, sicosyl or letraeosyl;

in the case of D: ethylene, dimethyethylene, butylethylene, octy;

ethylene, propylene, dimethyl propylene, butylprc pylene, octylpropylene or 1,2-cyclohexylene.

In the amide-amidine derivatives particularly suitable for the purposes of the present invention, either R ₁ or R ₂ denotes a t-alkyl group, ie an alkyl group of the configuration:

A.
A ^ O—— * (II)

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in which A. alkyl groups with a total of 3 Ms 23 carbon atoms, preferably 11 "to 23 carbon atoms. Particularly good results are achieved if this spatial configuration is present not only in one but in both E ₁ and R ₂ R ₁ and R _{2 represent} an alkyl group or mixtures of alkyl groups within the specified carbon range; this applies in particular if R ₁ and / or R _{2 have a} t-alkyl structure and contain commercially available compounds that are used to introduce this part into the molecule It is known that mixtures of various alkyl groups are particularly suitable among these compounds are those in which either R ₁ or R _{2 is} a mixture of t-alkyl groups having 12 to 1b, on average 13 carbon atoms, or a mixture having 18 to 24 carbon atoms. / ■ '... "

The group R is formed by addition polymerization of olefins having 2 to 12, preferably 2 to 5 carbon atoms; pure olefins are used for the polymerization. Such olefins are either gaseous or liquid under normal conditions and are im generally by cracking petroleum or other hydrocarbons won. Fractions, the olefinically unsaturated open-chain Hydrocarbons with very different molecular weights derived from olefins with * 2 to 12 carbon atoms, are readily available. Preferred are olefins which contain 2 to 5 carbon atoms; are best suited Olefins with 4 carbon atoms. It is of course best to use relatively pure olefins which will remove sulfur, cyclic compounds and other impurities have been.

You can use mixtures of the various olefins from ethylene to for dodecene, but also use the individual olefins. With special Advantageously, one uses olefin mixtures, the components of which are from Ethylene range up to pentene, even better mixtures of the different Butene. The butenes commonly used include both straight-chain and branched-chain isomers. It is possible and

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often desirable to use a particular isomer, e.g. isobutylene, With regard to the present invention, the separation of a particular isomer is not important. Rather, you can Mixtures that are readily available industrially can readily be used for the purposes of the present invention. The starting point At normal temperatures, the olefinic polymers used in the materials used can be anything between easily mobile and fairly viscous have liquids.

Olefin polymers suitable for the purposes of the present invention ^ are derived, for example, from ethylene, propylene, isobutene, 1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene, 1-oetene, 2-octene, 1-decene, 1-dodecene and 2-dodecene.

In structural formula I, the substituent R is bonded to a specific carbon atom. It is easy for a person skilled in the art to see that the substituent R can also be on the carbon atom to which the cyclic amidine is bonded. The substituent R arrives by converting maleic anhydride into the molecule and, as a result, can be linked to that in the α-position to the carboxyl group as well to the carbon atom in ß-position to the carboxyl group be bound. In the context of the present invention, this is a matter of fact Taken into account.

The polyolefin is first treated with maleic anhydride at temperatures from about 200 to 2 ° C implemented. The implementation requires about 6 to 16 hours. The maleic anhydride is used in excess, namely in about 1.5 to 3 times the amount over the stoichiometric amount. By using an excess of maleic anhydride you can see increase the yield. The polyolefin reacts with the maleic anhydride to form a succinic anhydride derivative which can be separated from the excess maleic anhydride by vacuum distillation or a corresponding treatment. The product can be diluted with xylene or a similar solvent and filtered.

90 983 9/12 44

Bas olefin succinic anhydride is then combined with a compound the formula

(III).

implemented. You order "etsung will tie at a temperature of about 200 ⁰ O O, preferably 60 ° ö Ms 12ü performed.

In the reaction between the amine and the poly [lkenyl succinic anhydride] a half-amide of the formula is obtained

OR ₁ R ^ ÖH - <y ar (17)

CH ₂ -GOOH

This hemiamide (IV) is then combined with a compound of the formula

H- '-V H ₂ (V)

reacted by heating the mixture to reflux. You implementation can be carried out without a solvent if necessary; In general, however, one works with solvents. In the latter If necessary, inert aromatic compounds such as benzene, toluene, xylene, etc. can be used as solvents. Toluene and xylene are preferred if higher molecular weight reactants are used, will. The implementation takes place at the boiling point of the mixture and continues until 2 moles of water per mole of acid have been removed * Sas water is made by distillation or if a solvent has been used, removed from the reaction mixture by azeotropic distillation. You will respondents in equi-r molecular amounts used; if necessary. You can use the amine in excess use. If you work with an excess of amine, the highest To achieve possible yields, βο must be the remaining excess can be removed by distillation under reduced bridge.

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Small amounts of excess amine do not need to be removed » because they do not affect the utility of the amia-amidine product.

The yields of amide-amidine derivative of polyalkenylsuccinic acid are generally between 7? and almost

The following can be used as Amin4e for the reaction: ethylenediamine, diethylenetriamine _t triethylenetetraamine, hydroxyethylethylenediamine, propylenediamine, dipepylenetriamine, tripropylenetetraamine or hydroxyethylpropylenediamine.

Examples of R-substituted half-amides (17) are "H-butylberasteinaäurei K _f ίί-diootylberDBteinsäure-, N-octylberasteinsaure-r N-dodecylsuccinic acid-j N-octadecylsuccinic acid, N-phenylsuccinic acid- or N-benzylsuccinic acid in these half-succinic acid- or N-benzylsuccinic acid en is a polyalkenyl group such as polybutenyl, polyootenyl, polydeoenyl or polydodecenyl, which have molecular weights between about 4UO and 3UOU *

The compounds prepared as described above are used according to the invention as dispersants for lubricating oils and fuels. The compounds are used in amounts of about U, uOr> up to 15 percent by weight based on the lubricating oil or heating oil or fuel, and we add them to these products in a known manner. In fuels they are preferably used in amounts of 0.15 to 5/61, even better 0.01 to 2 _%, based on the weight of the same. They are used in lubricating oils in amounts of 0.1 to 15%, preferably 0.1 to 10%, based on the weight of the lubricating oil or lubricant. The compounds according to the present invention have, as has been found by numerous known test methods, excellent action as dispersants in lubricating oils and fuels.

At the fuels of the type contemplated herein is those having a boiling range from 23.9 ° to 399 ⁰ C, insbesonden to gasolines, jet fuels, diesel oils and heating oils. The compounds are particularly useful for fuels with boiling points up to 316 ⁰ O, ie for normal gasoline and jet fuels. -, {

909839/1244 bad original

The lubricating oils considered according to the invention can be both mineral oils and synthetic oils. Both mineral oils may involve naphthenic or paraffinic üle or also mixtures of these two act, wherein Diss viscosities of between 1 to 25 centistokes may be 100 G ^0. It can be distillates or mixtures of neutral or bright stock oils. If necessary, the lubricating oils can be stocked or gelled and used as solid lubricants. In terms of oils, all forms are possible, from spindle oils or hydraulic oils to Qelen for the drive of aircraft engines. It can also be oils for spark-ignited internal combustion engines as well as for compression internal combustion engines with the ratings SAJ1. 3 to SAE bO. Furthermore, lubricating oils of the type of hydraulic and automatic transmission fluids come into consideration.

Synthetic lubricating oils contemplated here include Esters, such as dioctyl, dinonyl or diisodecyl adipates, azelates or -sebacate as well as polyethers and silicones. Does the in Considered oils around hydraulic fluids, so can that Base oil also contain phosphate esters.

The additives of the invention can also be added to base oils, DIE transmission fluids, hydraulic fluids, gear * iy & i or represent -lubricating.

Together with the additives proposed according to the invention köaneir- ^ atibh still other additives (these other additives söWi'e 'those of the kind considered here are often called Additives), as well as e.g. antioxidants, antifoam agents, rust inhibitors, anti-rust agents, agents, • the oils to be used under difficult conditions were added will. Pour point depressant, means to improve yiskosity * iEdexesA.ä. For example, one or more dithiophosphates can be used such as zinc, barium or mekel dialkyldithiophosphate, sulfurized Oils such as sulfurized sperm oil and sulfurized terpenes, Phenoles SuI- "fide, -Alkylarylsulfonate, Petroleum sulfonates (normal or such

Keserve) 'such as calcium, Bariioi- or "-Strontiumpetro-

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Leumsulfonate, polymers and copolymers from: alkyl acrylates, ^ lates, -itaconaten, -fumaraten or -vinylesrboxylaten or mixtures of these compounds, copolymers of acrylic acid esters and polar monovinylidene compounds such as H-yinyl-2-pyrroliäott,? inylpyrdines, aminoalky / acrylates or -methacrylates or polyethyleneglyc "olaei $ a> acid esters, polybutenes, alkylphenolalkylene oxide condensates, alkenylsuccinic anhydrides, various silicones and alkyl or aryl phosphates such as tricresyl phosphates. 4,4'-methylenebis-2,6-di-tert-butylphenyl,! Erialkylphenols, tris (dimethylaminomethyl) phenol, phenothiazine _f üfaphthylamine, ST'-sec-butyl-N, Nd ir methyl-p-phenylenediamine, alkaline earth salicylates, calcium phenyl stearate, P alkylamines, in particular C ₁ 2- ^ 24 ~ ^{Al: k: yl family} » ^Ο 7 ^ο ^ - ^ίΒΟ ^ ^@ Amines, alkyl or aryl imidazolines and alkenyl succinic anhyarides, which are reacted with amines and then with boron compounds such as boron oxide, boron halides or boric acid esters , add.

A lubricant for turboprop engines can be produced by mixing the copolymers according to the present invention with di-2-ethylhexyl sebacate and a mixture of biyesters obtained by condensation of 2-ethyl-1,3-hexanediol and sebacic acid with 2-ethylhexanol, an average of 5 glycol units per molecule is obtained. The mixture can also contain an antioxidant, a stabilizer or other additives.

The following test methods were used to test the connections used according to the present invention.

Dispersion test ...

. The dispersing action of the compounds according to the present invention was determined using a method based on the dispersion of asphaltenes in typical mineral oils. The related to the test method Asphaltjaene were prepared by a naphthenic oil with air under the influence of a trace of iron salt as Perrinaphthenat as catalyst oxidized * The oxidation is carried out at 175 ⁰ O, and that is introduced at this! Demperatur 72 hrs. Airflow by a naphthenic oil. Pentane is added to the cooled, oxidized oil to form a solidified mass. The solidified mass can be separated by centrifugation and by extraction

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with Ptntan τοη 01 freed wtrdtii. It is then used with chloroform * recorded; the constant solution is based on the content of nitrogen τοη rfcw * 2 * (Gtw./Tol.) tingtsttllt »

Should the connection be checked for its inspection, to is lie in a standard oil, a.B. tinem solvent-titrated 100 neutral oil dissolved. Mieohungen are then made which contain different amounts τοη about 2 to Q.01 Jf or even less of the compound in the oil.

A sample of a mixture is treated with 1 ml of the standard solution of asphalt in chloroform. The sample and reagent are carefully mixed in a test tube; thereafter, the test tube is placed in convection ovens eihen and left there at 90 ⁰ O swti hours to drive off the volatile material. The test tube is then allowed to cool and the appearance of the sample is assessed.

If the tested compound has a dispersing effect, it will Oil may appear colored but clear.

"Read Panel Ooker" .

This method is described in the documents of the "Fifth World Petroleum Congress" (1959) in a work by RM Jolie "Laboratory Screening Test for Lubricating Oil, Detergents and Dispersants". | A sample of a compound to be tested is dissolved in a 170 SUS solvent-extracted mid-continent neutral oil which contains 1 ^ of a thermally unstable zinc dialkyldithiophosphate. The mixture is placed into a heated oil sump and injected two hours against a plate which τοη at a temperature of 300 ⁰ G is held. The increase in weight of the plate is then determined. The weight gain is compared to that of a plate against which oil has been sprayed without the compound to be tested.

' Sundatrand-Pumpenteat "

In this test method for fuel oil distillates Mr. 1 fuel oil, which contains 4 g of synthetic mud ^m 7aem additive (additive) is treated. The oil is left for an hour through a Sundstrand

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Oil burner pump, which contains a sieve with a unit of 16UO mesh / oa ψ , circulate. The sludge deposit is collected and weighed, (HtlBon, Osterhaut and Sohwindeaan, Ind. Eng. Ohem., 48, 1892 (1956).)

Base formation test according to APIf MS-Teat Sequence YA With this test method, the base dispersion properties of a lubricant are examined under operating conditions at low and medium temperatures. A single cylinder oil test engine is operated under the conditions described in "ASTM Special Technical Publication No. 315". The engine can be tested at any time during the course of the test. Seven parts of the engine are examined for sludge deposits (GRO rating, 10 »clean). The seven parts examined are: rocker arm assembly, sipp arm cover, valve surface, timing gear cover, bumper cover, bumper chamber and oil pan *

The following examples serve to further illustrate the present invention.

example 1

A mixture of 1390 g of a 90 # solution of polybutenyl amber acid anhydride (made from maleic anhydride and polybutene with a molecular weight of 930) in xylene with an anhydride content of 0.720 mmol / g and 130 g of t-ootylamine are stirred for 10 hours at 10O ⁰ G get. The solvents and unreacted t-octylamine are then distilled off in vacuo; in this way the hemiamide is obtained as an intermediate (^ K = 0.90).

60 g of ethylenediamine are added to 690 g of this intermediate product and the solution obtained in this way is heated to HO ⁰ O for three hours using a water separator. A further 115 g of ethylenediamine ai is then added and stirring and heating are continued for a further 10 hours . At the end of this time, an analysis of the distillate in the water separator shows that practically the theoretical amount of water has been developed, which corresponds to complete imidazoline formation. The product is isolated by ^{distilling at 110 0} O under reduced pressure (JiN = 1.95).

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In the Panel Coker test, a mixture containing $ 1.5 of the above ^ n ^ it results in a deposit

»Weighted from 36 # gv ^ using the same oil but without the one above (described additives * this results in a deposit in the weight of 322 mg.

The Sundstränd pump test results in an amount of 0.015 g 'Mditive in 40 ml of oil a sludge deposit of 6 mgj in an oil Without an additive, a Schlanmift deposit of 230 mg results.

Example 2r ■ - ^ - ^ · '· ^; "'* ■'

A mixture of 1958 g ^{of polybutenylsuccinic anhyaride according to Example 1} I (made from polybutene with a molecular weight of 950) and 280.1 g of a commercially available mixture of t-alkylamines with 12 to 15 EÖhien material atoms, on average 13 carbon atoms, is at 95 ° 10 ° G 12 Stirred for hours until the formation of the half-amide is complete. 188 g of ethylenetriamine are then added to 2045 g of diosious intermediate product and the solution obtained in this way is refluxed using a water separator at 170 to 18 ° ^ Meaitilliι? ^ T ■> iv · ■ iwelohes ■■ äns ■ chli «ßeÄd ■ is filtered. The end product contains 5, * Φ JStf (fheoriei ^

In the; vPanel Goker; ^ dissolves results in a mixture that is 1.5 ^ of the levels described above. Product * contains a deposit weighing 21 mg. Without the additive, the oil results in a deposit weighing 322 mg.

In the Sundstrand pump test, Q, U shows 15 g additive in 100 ml OIL, a, .Sludge deposit of 4 mg, while an oil without an additive a Sludge deposit, from t7u mg. results.

1.5 ropes of the 'vors-tehehden' product are used together with a part of a commercial product to improve the viscosity index in 91.5 parts of a 1YO SUS solvent-extruded mid-oontinent new

909839/1244

tral oils mixed in. The viscosity of the mixture is 1006 ^{cSt. At 99 0} C and 60.50 cSt. at 38 ⁰ C; the viscosity index is 147, the ASTM pour point is at -34.4 ⁰ C. In the formation of sludge test (as described earlier) to am.Ende gives a 75stündigen operating time a Wert.für the sludging of 68.4 (70.0 = clean ). The value for control oil without additives is 40.2.

Three parts of the product according to Example 2 are mixed with 0.7 parts of 4,4'-methylenebis (2.6% of it-butylphenol), 1.0 part of trikresy-phosphate. 0.3 parts of sulfurized sperm oil and 5 parts of a commercial viscosity index improvement product are mixed into 90 parts of 170 STJS solvent-extracted mid-continent neutral oil. The viscosity of the mixture is 11.04 cSt. at 99 ⁰ C and 68.07 c St. at 37.8 ⁰ C; the viscosity index is 139. The ASTM pour point is -40 ⁰ C. In the formation of sludge test (as described earlier) of a 75stündigen operating time is obtained at the end IN_ value for the sludge deposition of 68.7 (70.0 = clean). The value for a control oil without additives is 40.2.

Example 3

A mixture of 1724 g of an 89% solution of polybutenylsuccinic acid anhydride with an anhydride content of 0.488 mmol / g (prepared from maleic anhydride and polybutene with a molecular weight of 1430) in 2ylene and 61.7 g of tr-butylamine are stirred for about two hours heated to 80 ^{° C.} The stirring at this temperature for a further 10 hours and sets during this period a further 60 g of "t-butylamine, to compensate for the result of the volatility of the material entering loss. Subsequently, the excess amine by distillation at 60 is to 7O ⁰ C and 0.2 mm removed three hours. An IR analysis of the product shows no content of unreacted anhydride. The nitrogen content is 0.97%.

A solution of 6- -1.9.9 _f g of this product and 13.0 g A'thylendiamin is heated for two hours 140 ⁰ C. A further 25 g of ethylenediamine are then added and the mixture is heated again to 14U ⁰ C. for eight hours while stirring. At the end of this time, the end product is recovered

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Distillation at 11O ⁰ C and 3 into 1 1/2 hours. The total nitrogen content is .1.970 (theory: 2.150); the basic nitrogen content is 0.800 (theory> 0.729t). The infrared spectrum confirms the presence of both amide and imidazoline.

Ia Aephaltentest are 0.2 £ Aaphaltene with only 0.20 of the standing egg Compound dispersed.

In the Panel Coker Test, a mixture with 10 of the above-described product resulted in a deposit weighing 14 mg. Without additives, bass yellow oil results in a deposit weighing 322

In the Sundstrand pump test, the sludge weight is 0> 013 g Additive in 100 ml 01 6 mg, whereas an oil without an additive results in a sludge deposit of 230 mg.

1.6 parts of the product described above are mixed together with a rope of a commercially available zinc dialkyldithiophosphate and 6 parts of a commercially available product to improve the viscosity index in 91.4 parts of a 170 SUS solvent-extracted mid-continent neutral oil.The viscosity of the mixture is 11.21 cSt . at 199 ⁰ C and 61.95 c St. located at 37.8 ⁰ C at a Tiskositätsindez of 147. The ASTM pour point of -34.4 ⁰ C. The mixture is subjected to the above-described Sohlammbildungstest; At the end of a 7f? hour operating period, the result for the formation of the bottom ridge is a value of 68.5 (70.0 = clean). The value for a control oil without additives is 40.2.

1 1/2 parts of the product according to Example 3 are mixed with one part of psenothiazine and one part of tricresylphoephate in 96.5 ropes of bis-2-ithvlhezylsebacat. The liquid is subjected at 174.6 ⁰ C the corrosion and Oxidationsbeständigkeitetest governed according to "federal test Mtthod Ho. 5308" which is lugzeugturbinenaotoren vorgeeohrieben for lubricating oils specification MIL-L-78Ü8 for?. The appearance of the oxidation tubes is generally an indication of their use. Oiling without additives.

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Example 4

A mixture of 3356 g of polybutenyl succinic anhyärid according to i ^ Example 3 and 237 g of t-octylamine are heated to 110 Μβ. · 42α-9ον heated so that - after vacuum distillation - the Haihamid formed as an intermediate product with a nitrogen content of D, 75 $ (theory = »O.79 #) is present.

32.5 g of N-hydroxyethylethylenediamine are added to 442 g of this halhamide and 100 g of IyIöl; the solution thus obtained is made using a Water separator heated to reflux for 15 hours at 150 to 16 ° C. At the end of this time the water separator contains $ 91 the theoretical Amount of water, based on a complete implementation. After removal the volatile constituents by vacuum distillation, the product is filtered. Its nitrogen content is 1.9496 (theory = The infrared spectrum confirms the amide-ajaidin structure.

In the Panel Coker test, a mix gives 1.5p of the above Product contains a deposit weighing 42 mg. Sass same oil without addition results in a deposit weighing 322 mg.

In the Sundstrand pump test, 0.015 g in 100 ml of oil produced a Sludge deposits weighing 3 mg, while in the case of an oil without an additive the weight of the sludge deposit is 230 mg.

Three parts of the above amd-amidine product are mixed with 5 parts of a commercial additive for automatic transmission fluids, namely Lubrizol 280 and 4.5 parts of a commercial compound to improve the viscosity index in 87.5 parts of a base oil with a viscosity of 4.0 cSt. at 99 ⁰ C and a viscosity index of 95 mixed in. The mixture obtained has a viscosity of ¹ JScSt. at 99 ^° C.

The mixture is tested under the conditions of the test method "Federal Test Method 5308" at 149 ⁰ C. Subject 300 hours you can see in the paper stain test that the sludge is dispersed. A corresponding test with a liquid without the above product had to be discontinued after 72 hours.

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Example 5

A mixture of 1724 g of polybutenylsuccinic anhydride according to Example 3 and 93 g of fresh, distilled aniline is heated to 60 to 80 ° C. for two hours while stirring. The formation of the intermediate Halbamidswird by the disappearance of Anhyäriäspitzen in the infrared spectrum displayed "To 433 g of the intermediate product is one then 32 g of diethylenetriamine and 100 g of xylene;. .The mixture using a water separator for 12 hours at 150 to 160 ⁰ C for Heated to reflux. Am? End of this time the volatiles at 150 ⁰ C under reduced pressure äbdestilliert, so as to obtain the desired product -If 0 # = 2.25).

In the Panel · Goker Test, a mixture gives 1.b% of the above Product. Contains a deposit weighing 32 mg. Same oil without addition results in a deposit weighing 322 mg.

In the Sundstrand pump test, 0.015 g in 100 ml of oil produced a Sludge deposits weighing 16 mg, while in the case of an oil without an additive the; Weight of the sludge deposit is 230 mg.

Example 6

A Mischürig * äiiö 1724 g Polybuteny succinic anhydride according to Example 3 and 19ÖV7 g of a commercial mixture of t-alkylamines having 12 to 15 Kohlelistöffatomen, an average of 13, is heated with stirring for 20 hours at 15O ⁰ G!; after this time the anhydride is in that

- • has been converted to what is indicated by the infrared analysis Solution from 918 g of the hemiamide and 46.3 g of 1,3-propylenediamine

cm- xylene using a water separator at 150 ⁰ C 1b stood heated to reflux. At the end of this time, the almost theoretical amount of water has accumulated. The volatiles are removed by destination under reduced pressure at 150 to 170 ⁰ G; the product is filtered (? έ Ν = 2.3).

In the Panel Goker test, a mix results in $ 1.5 of the above Product contains a deposit weighing 42 mg. Same oil without addition results in a deposit "weighing 322 mg.

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In the Sundstrand pump test, υ, υ15 g in 10μ ml Ql result in a Sludge deposits weighing 16 mg, while in the case of an oil without an additive the weight of the sludge deposit is 230 mg.

Example 7

A mixture of 1832 g of a 89 # solution of Polybutenylbernstein anhydride in xylene content of 0 with an anhydride, ^ 46 mmol / g (prepared from maleic anhydride and polybutene with a molecular weight of 1430) and 45 E dimethylamine in an autoclave for 8 hours 50 ⁰ C heated. At the end of this time the initial pressure had dropped to 0; the infrared analysis no longer showed any anhyaride content. 30 g of ethylenediamine and 150 cm of xylene were added to 841 g of the hemiamide thus formed. The resulting solution was refluxed for 10 hours with stirring and using a water separator. At the end of this time, a further 60 g of ethylenediamine were added and the reaction continued for a further 6 hours. The product was isolated by vacuum distillation and filtration ($ N = 2.1).

In the Coker Reading panel, a mix results in $ 1.5 of the above Product contains a deposit weighing 33 mg. Same oil without addition results in a deposit weighing 322 mg.

In the Sundstrand pump test, 0, over 15 g in 1 (JO ml 01 a Sludge deposit weighing 65 mg, while an oil without additives set the weight of the sludge deposit is 230 mg.

Example 8

A mixture of 2958.3 g of polybutenysuccinic anhydride according to Example 7 (prepared from polybutene with a molecular weight of 14301 and 320.9 g of a commercial mixture of t-alkyl amines with 12 to 15, on average 13, carbon atoms is stirred for 15 hours to 90 to heated 100 ⁰ C. After this time, the formation of the half-amide is completed, which is reflected by the disappearance of the anhydride bands in the infrared spectrum. to 517 g of the intermediate product gives you 32.8 g diethylenetriamine (25 $ sulfuric excess) and heat the resulting solution using a water at 150 to 160 ⁰ C for 16 hours to reflux. at the end of that time have INS

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a total of 8.36 g of water formed (theoretical amount = 9.0 g). The final product is obtained by removing the volatile constituents Separate vacuum distillation and filter the residue (# ET = 2.14).

In the Panel Ooker Sest, a mix that makes $ 1.5 of the above Product contains a deposit weighing 48 mg. Same oil without addition results in a deposit weighing 322 mg.

In the Sundstrand pump test, 0.015 g in 100 ml of oil resulted in a sludge deposit weighing 4 IQg _1, while with an oil without additives the weight of the sludge deposit was 200 mg. amounts to.

1.5! Parts of the above product are made with a rope of a commercially available zinc dialkyldithiophosphate and 6 ropes of a commercial! conventional product to improve the viscosity index mixed into 91.4 parts of a 170 SUS solvent-extracted Mid-Gontinent neutral oil. The viscosity of the mixture is 11.21 cSt. at 99 ⁰ G and 62.17 cSt. at 37.8 ⁰ C at a viscosity index of 146. DerASSM pour point is at -34.4 ⁰ C. The mixture is subjected to the formation of sludge test described above; At the end of a 75-hour operating period, the sludge formation is 68.6 (70, 0 = clean). The wetft for an Eontrollol without additives is 40.2 "

In another test, 1.5 ropes of the product described above with a rope of a commercial zinc dialkyldithiophosphate, :: ■ 6 ropes of a commercial product to improve the viscosity index and 2 ropes of a basic calcium sulfonate in 89.5 ropes of a 170 SUS solvent-extracted Mid-Oontitnent neutral oils mixed in. The viscosity of the mixture is 11.58 cSt. at 99 ° G and 65.62 oSt. ' ! at 37.8 ⁰ G at a Viscous · tätaindex of 145 "The mixture is subjected to SchlaambiiäungsteBt described above; Approximately 75 hours of operation results in a value of 68.2 (70.0 = clean) for the silt lamb formation. The ¥ ert for a control ?! without additions is 40.2.

009839/124 ^
- 18 -

BAD ORJGINAL

Example 9

A mixture of 1832 g Polybuteny! Succinic anhydride according to Example 7 and 84 g of piperidine is heated with stirring at 70 to 80 ⁰ C, up to a sample of the infrared analysis icein Anhydridabsorption can be determined more. A rope of the intermediate product is then treated in two stages in the manner described in Example 1 with ethylenediamine. After isolation in the usual way, the product shows a nitrogen content of 1

In the Panel Coker! Test, a mix that gives 1, b # of the previous one gives Product contains a deposit weighing 32 mg. Same oil without addition results in a® deposit weighing 322 mg «

In the Sundstrand pump test, 0.015 g in 100 ml of oil produced a Sludge deposit weighing 9 mg, while with an oil without additives the weight of the sole sludge deposit is 230 mg.

Example 10

A mixture of 1851 g of an 80% solution of polybutenyl succinic anhydride in xylene with an anhydride content of 0.270 mmol / g (manufactured from maleic anhydride and polybutene with a molecular weight of 1780) and 99 g of a commercial mixture of t-alkylamines with 12 to 15, an average of 13 »carbon atoms will be under

_o heated

Stir for 10 hours at 130 G. After this time, the infrared analysis shows no more anhydride bands in the solution. 45.6 g of triethylenetetramine and 2üu cnf of xylene are added to 790 g of the hemiamide solution thus obtained. The resulting solution is heated using a water separator at 150 to 160 ⁰ C to reflux, until an analysis of the liquid in the water separators, indicating that the evolution of water has ended. The desired product is obtained by distilling off the volatile components of the mixture in Yakuum at 150 ⁰ C (Joet = 1.9).

In the Panel Coker test, a mix that gives $ 1.5 of the above results Product contains a deposit weighing 40 mg. The same oil without addition results in a deposit weighing 322 mg.

In the Sundstr-nd pump test, 0.015 g in 100 μl of oil gives a

909839/1244

- 19 - BATHROOM

Sludge deposit weighing 5 mg, while in the case of an oil without an additive the weight of the sludge deposit is 230 mg.

Example 11

The half-amide of polybutenylsuccinic acid anhyäriä according to Example 1u and a commercially available mixture of t-alkyl amines with 18 to 24 carbon atoms is prepared in the manner described in Example ^. A solution of 819 g of the hemiamide and 23.2 g of 1,2-propylenediamide is ^{refluxed with 200 cm 5 of} xylene at IbO ⁰ C for 18 hours, the water which separates out being collected in a separator. After removal of the volatile components in vacuo, the product has a nitrogen content of 1.9 ^{at It) O 0 G and after filtration.}

In the Coker reading panel, a mix results in the 1, b # of the preceding Product contains a deposit weighing 30 mg. The same oil, without addition, gives a deposit weighing 322 mg.

In the Sundstrand pump test, 0.015 g in 100 ml of oil produced a Sludge deposit weighing 11 mg, while with an oil without an additive the weight of the sludge deposit is 230ng.

Example 12

The hemi-amide made from polyoctenyl succinic anhydride and t-butylamine is prepared by adding 2518 g of polyoctenyl succinic anhydride (anhyaride content = 0.397 mmol / g, made from maleic anhydride and poly- ^ i-pcten,, with a molecular weight of 1800) and 73 g of t-butylamine bO G implements six hours. A further 73 g of t-butylamine are then added and stirs. and heated for a further 10 hours. At the end of this time it results No anhydride content can be found in the infrared analysis.

For this intermediate product is prepared by two-stage treatment with an excess of ethylene diamine at 140 ⁰ C in the besehrie in Example 1 Beneh operation of an imidazoline forth. The product contains 1,

In the Goker reading panel, a mix results in the 1, b # of the preceding Product contains a deposit weighing 27 mg. Same oil Without any additive, it produces a deposit weighing 322 mg.

909839/1244 ■ "_-- ■ <■.

BATH ORIGINAL - 20 -

In the Sund strand pump test, 0.01 i? g in 10u ml of oil one Sludge deposit weighing 10 mg, while in the case of an oil without an additive the weight of the sludge deposit is 230 mg.

In order to show the effect of the products according to the invention as high-temperature dispersants, 1.4 parts of the product according to Example 8 in 98.6 parts of an SAE 30 base oil, soft 0.08 $ zinc in the form of a zinc dialkyldithiophosphate and 0.15 $ calcium in Fora contained a calcium sulfonate having an excess of base. The viscosity of this mixture was 12.93 cSt. at 99 ⁰ O and 135.8 cSt at 37.8 ⁰ C.

This mixture is tested in the caterpillar tractor L-1 test. The exam is carried out with a fine single-cylinder caterpillar engine that is connected to two new pistons, rings and liners were fitted and 480 hours at 1000 HpM with an average load of 19 »2 hp and an oil sump temperature of 64.5 to 65.1 ° C was operated. Of the related fuel contained $ 1 sulfur. The test method serves as a Measure of the dispersibility of the oil. The tests were carried out after 120, 240, 360 and 480 hours. At the end of the attempt white piston in the upper groove 0 $ carbon deposit and none Lacquer formation below the first ring groove.

If the same oil is used without an additive according to the present invention subject to the same test, this is shown by an inspection 120 hours with a 4 # carbon deposit on the upper groove strong lacquer formations in the second and third ring grooves and the first piston surface. Such a liquid meets the requirements of the standard test (MIL-L-2104A), whereas a liquid, which contains a product according to the present invention meets the requirements of this test method.

909839/1244

Claims (5)

Claims 1) The use of a dispersant in lubricating oils and fuels, characterized in that the dispersant consists of a compound of the formula —C—— η. .is _t in which. R an Älkenylrest kit about 30 to 20ü carbons, E ₁ alone is an alkyl radical with 1 to 24 carbon atoms, or a phenyl, capthyl, benzyl or alkyl substituted one Phenyl, naphthyl or benzyl radical, where in - ^ the latter the alkyl substituents a total of up to 24 Contain carbon atoms, hydrogen alone or alkyl with 1 to 24 carbon atoms, R ₁ and Ro together with the nitrogen atom to which they are attached form a morpholine, thiamorpholine, piperidine or pyrrolidine ring,. . > R, hydrogen, 2-hydroxyethyl, 2-aminoethyl, 2-hydroxypropyl " ^a " - 3-hydroxypropyl, 2-aminopropyl, 3-aminopropyl, 2- (2-aminoethyl) aminopropyl or 3- (2 * aminoethyl) aminopropyl and D a® divalent saturated chain of 2 to 5 'carbon. ^ atoms whose valences are available through hydrogen atoms or alkyl groups with a total of 12 carbon atoms or V '■ ^: -; ^ - ■ - ^ ■■■ iΣόaιbillatioπe "Ä-" ■ ^; τön. Hydrogen atoms and alkyl groups with;. ..,. ν i ^ ß a total of .12 carbon atoms or a 1,2-cyclohexylene ^ '"residue are saturated,, _? 2) DIt use of a dispersant according to claim 1, characterized characterized in that R of © inea olefin having 2 to 5 carbon atoms is derived " :. .309839 / 1244: .-,: _{i; BAD} ai ' -Z- 3) The use of a dispersant according to claim 1, characterized characterized in that R is derived from an olefin having 4 carbon atoms. 4) The use of a dispersant according to claim 1, characterized in that at least one of the two substituents R ₁ and R _{2 represents} a t-alkyl group having 4 to 24 carbon atoms. 5) The use of a dispersant according to claim 1, characterized marked that R is derived from an olefin having 2 to b carbon atoms is, R «. and R _{2 is} a t-alkyl group having 4 to 24 carbon atoms represent,
D ethylene and
r "is aminopropyl or aminoethyl. for Rohm and Haas Company Philadelphia, PA., V.St.A. 909839/1244