DE1644907A1 - Lubricating oil - Google Patents

Description

DR. ELISABETH JUNG, DR. VOLKER VOSSIUS, DIPL.-IN

PATENTANWÄLTE 8 MÖNCHEN 23 ■ S I E G E S T R AS S E 26 ■ TELEPHONE 34 50 67 · TELEGRAM ADDRESS: I N V ENT / M DN C H EN

Excretion from. March 13, 1968

P. 14 44 856.7 ^Be Ao

-V

u.z .: D 161

The Lubrizol Corporation, Cleveland (Ohio), V.St.ν.Α

"Lubricating oil η

Priority: August 18, 1961 from U.S. Patent _{Application No. 1} 132 3o5 and April 6, 1962 from U.S. Patent Application No. 185 52o

The invention relates to lubricating oils with an addition of new, oil-soluble nitrogen-containing hydrocarbon-substituted succinic acid derivatives, which are particularly suitable as lubricants for internal combustion engines, gears and power transmissions.

The French patent specification 1,254,094 discloses reaction products of hydrocarbon-substituted succinic acids

ORIGINAL INSP £ GT £ D

16U907

or succinic anhydrides whose substituent is more than Has 5o carbon atoms, with ethylenediamine, such as ethylenediamine, diethylenediamine, $ riethylenetetramine and. Tstraäthylenpentamin known, the ice lubricant additives in particular siar. Reduction of sludge formation in internal combustion engines and crankcases, especially with alternating high and low working temperatures and as a dispersing agent in Lubricants based on hydrocarbons are effective.

It has been found that similar additives derived from hydrocarbon-substituted succinic acids with other amines associate similar effects with certain advantages.

The lubricating oil according to the invention, containing a kohlenwaeseretoff-substituted succinic acid derivative of an etioketoffhaltigen compound is characterized in that it is a. Contains succinic acid amide, amidine, imide or ammonium salt, that from a succinic acid derivative of the general Porael

Ζ ·· '' - '■' ■■ ... 0 · 's ■

■■■ "■■ - /

R-CH-C-X

CH ₂ - CX. . . 0

where A is a hydrocarbon radical with at least 50 aliphatic carbon atoms and X is a halogen atom, a hydroxy, alkoxy or aoyloxy radical, by means of utilities

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Ammonia, an aliphatic amine, an aromatic, heterocyclic or carbocyclic amine or polyemine or their hydroxy-substituted derivatives, a hydroxyalkyl-substituted one Alkylenamine, a urea »thiourea, Hydrazine, guanidine, amidine, amide, thioamide or Cyanamide has been produced.

The effectiveness of these products in terms of the properties which they impart to a lubricant depends largely on the chain length of the hydrocarbon substituent in the Bern * stinic acid residue from which the products are derived.

Products in which the hydrocarbon substituent is longer than 50 aliphatic carbon atoms give a lubricant » agent with anti-oxidant and anti-corrosion properties as well as cleaning properties. In addition, it was found that the cleaning property th of the products decrease sharply with decreasing chain length of the hydrocarbon f-substituent, the less than 5o contains aliphatic carbon atoms, so that products that less than 35 aliphatic carbon atoms in this substituent as cleaning additives in lubricants are ineffective

The additives can be added to lubricating oils of synthetic, animal, of vegetable or mineral origin are added, Mineral lubricating oils are easy to access because of their * its excellent properties and low cost

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preferred, but oils from the other groups can also be preferred for certain applications. For example, synthetic polyester oils such as didodecyl adipate and di-2-ethylhexyl setoacate are preferred as lubricants for jet machines. The normally preferred lubricating oils are liquid oils with a viscosity range from 4o SUS at 38 ⁰ C to about 2oo SUS at 99 ⁰ C,

The concentration of the nitrogen-containing reaction products as lubricant additives is usually 0.1 to 1 o percent by weight. The optimum concentration for a particular application depends largely on the working conditions, where the lubricant is subjected * For example, is the additive in lubricants for gasoline internal combustion engine about 0.5 to 5 $, in such a gearbox and Dieselmaechinen he can loft it or amount even more.

There may also be other additives in the lubricants e.g. additional cleaning agents from the ash-containing Type, gowns that improve viscosity index, stook point depressants Agents, antifoam agents, high pressure additives and rust, oxidizer and corrosion preventive agents.

In addition to the additives according to the invention, the lubricating oils can also contain metallic cleaning additives in amounts of 0> t

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contain * Pure some areas of application, e.g. in lubricants for marine diesel engines, can also 3ö ^ metallic cleaning agents are used. tuck Lubricants can also use extreme pressure additives, means for Improvement of the viscosity index and those to lower the pour point in amounts of 0.1-ioSt

The hydrocarbon substituent of the succinic acid amide B, -amidines, -imides or -ammonium salts can have polar groups contain »but only to the extent that the hydrocarbon character of the substituent does not change significantly | will. The polar groups can e.g. chlorine, bromine, keto, Ether, aldehyde, nitro groups, etc. The upper limit for the polar groups is about 1o # of the weight dee hydrocarbon antails.

The Kohlenwaaserstoff-Subetituenten are mainly of high molecular weight saturated petroleum Pra ACTIONS and aue saturated olefin polymers, particularly those with 2 to 3o C atoms, eB of 1-monoolefins such as ethylene, propene, 1-butene, i isobutene, 1-hexene , 1-Ooten, 2-Hethyl-i-hepten, 3-Cyclohexyl-1-butene and 2-Ethy 1-5-propy 1-1-hexene. Polymers of middle olefins, that is, those in which the double bond is not terminal, can also be used. Examples are 2-butene, 3-butene, 3-Ptnttn and 4-octene.

T ^ tSQSY $ 1 70

The substituents are also known from copolymers of the above Olefins with other copolymerizable olefinic substances such as aromatic, cyclic and polyolefins, e.g. from copolymers of isobutene and styrene, isobutene and Butadiene, propene and isoprene, ethylene and piperylene, isobutene and chloroprene, isobutene and p-methylstyrene, 1-Ηβχβη and t, 3-hexadiene, 1-ooten and 1-hexene, 1-heptene and 1-pentene, 3-methyl-1-butene and 1-octene, 3,3-dimethyl-i-pentene and 1-hexene, isobutene and styrene and piperylene, etc. come "

The proportions of the mono-olefins to the other monomers in the copolymers from which the sub stituent R is derived influence the stability and oil solubility of the end products made from them. Therefore, the substituent R derived from copolymers should be essentially aliphatic and saturated, i. at least 8 o? ί, preferably at least 95 #, should come from aliphatic monoolefins and no more than 5 # of the covalent CC bonds should be olefinic. In most cases this proportion will even be less than 2f> .

Specific examples of these are the copolymer of isobutene and 5% styrene, the telomer of 98 % isobuteno with 1% of piperylene and 1% of chloroprene, the telomer of 95% isobutene with 2 ^ 1-butene and 3f 1 -hexene, the telomer of 60 ^ isobutene 2ojt 1-pentene and 2o? (T-ooten, the copolymer of

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1-hexene and 2o # 1-heptene, the telomer of 9o $ isobutene with 7 $ cyclohexene and 8 # propene, the copolymer of 8o # ethylene and 2o # propene, etc.

The substituent B can also be from saturated aliphatic hydrocarbons, such as highly refined high molecular weight White oils or synthetic alkanes are derived from the hydrogenation of high molecular weight olefin polymers or others olefinic substances are obtained.

Preferred are from olefin polymers with molecular weights of approx. 75o - 5000 derived substituents. Olefin polymers with molecular weights of 1o ooo - Too ooo or higher the products according to the invention, also improving properties in terms of viscosity index. Their use is therefore often desired.

They nitrogen-containing group of succinic acid derivatives is derived from substances that are generated by a heat the structure -ICH are marked. The two free valences of the nitrogen atom are preferably due to hydrogen or via direct K-C bonds through amino «or organic residues saturated. Therefore belong on the connections with the nitrogen-containing group mainly ammonia, aliphatic aromatic, heterocyclic or carbocyclic Amines. You can use primary, secondary amines or even polyamines be like arylene amines, cyclic polyamines and hydroxy

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substituted derivatives of them.

Its imine these types are methylamine, ff-methylttthylamine, lf-methyl-octylamine, N-cyclohexyl-aniline, dibutylamine, cyclohexylamine aniline, di- (p-methylphenyl) amine, dodecylamine, octadecylamine, o-phenylenediamine, NN ^! -Di-nbutyl-p-phenylenediamine, morpholine, piperazine, a? Etrahydropyrazine, indole, hexahydro-1,3,5-triazine, 1-H-1,2,4, triasol,, bite- (p-aminophenyl) - methane, phenyl-methylenimine, cyclohexamine, I ^ jrrrolidin, 3-amino-5 »6-

diphenyl-1,2,4-tria2ine, ethanolamine, diethanolamine, quinone-diimine, 1,3-indane-diimine, 2-octa-decyl-imidazolidine, 2-f ^5- henyl-4-methyl-imide-zolidine, oxazolidine and 2- Heptyloxaisolidine, piperazine and araino-alkyl-substituted.

Hperazine, 2-heptyl-3- (2-aminopropyl) imidazolidine, 4-Methyliiaidaaoliain, 1,3-Bie (2-aminoethyl} imidazolidine lyrimidine, 1- (2-iminopropyl) piperazine, 1,4-bis (2-amino ~ ethyl piperazine and 2-methyl-1- (2-aminobutyl) piperazine

Alkylenamines which are hydroxyalkyl-substituted one or more times on nitrogen are also used. The hydroxyalkyl groups preferably contain fewer than 6 carbon atoms. Examples of such amines are N- (2 ~ hydroxyethyl) ethyl © m-diamine, N, N ^f -B'is (2-hydroxyethyl) ethylenediamine, 1 »{2 ~ ethyl} piperazine, hydroxypropyl diethylenetriamine, 1 _P 4- Bis (S-hydroxypropylJpiperazine, di-hydroxypropyltetrafethyl ^ a pentamf, N (3-hydroxypropyl) tetramethylenediajaine, 2-heptadocyl-1 - (2-hydroxyethyi) imidagsol in.

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Higher homologues "obtained by condensation of alkyleneamines or hydroxyalkyl-alkyleneamines via amines" or Hydroxy radicals are also usable * Condensation Via amino radicals leads to a higher amine below Release of ammonia, which leads to hydroxy radicals to products with ether bonds, releasing water

The nitrogen-containing groups can also be formed from ureas "thioureas, hydrazines, guanidines" amidines "amides" Xhioamiden "cyanamides, etc. · i examples are such compounds are hydrazine, phenylhydrazine» NjN'-diphenylhydrazine "Ootadeoylhydrazin, benzoylhydrazine, urea, thiourea, N- Butylurea »tearic acid amide, oleic acid amide» guanidine »1,3-Dipheny! Guanidine, 1,2,3-tributylguanidine, benzamide in, octadeoamidine, N, N ^l -dimethylstearaiQidine» cyanamide, dicyandiamide, guanylurea, aminoguanidine etc. It can Mixtures of these amines and the alkylene compounds of the French Patent specification 1 254 o94 can be used «

The bond of a nitrogen atom in an amber residue yields an amide or imide structure, that at a Berneteineaureiaidreet yields an amidine structure, and that at a Succinoyloxyest the structure of an oärbonsauren Ammoniumealies.

The usual method for the production of this succinic acid derivative is based on the general formula of higher molecular, amber acid-forming compounds

B-CH -CX CH ₂ -CX

in the B a hydrocarbon radical with at least 50 aliphatic carbon atoms and X halogen, hydroxy, alkyloxy or Aoyloxy residues are at least half an equivalent of the Nitrogen compound which has at least one -NH group, usually by heating to above 80 °, preferably to loo - 25o ° C.

For easier control of the reaction temperature, the Use of a solvent such as benzene, toluene, naphtha, Mineral oil, xylene, η-hexane and others are often advantageous.

The exact proportions of salt, amide, irnide or amidine-like bonds in the product is usually not known and depends largely on the nature of the acid-forming group and the nitrogen-containing compound and also from the reaction conditions, a, B. the temperature. For example, the reaction leads to «wipe the acid or their »anhydride and a compound containing aainos ticket off at relatively low tea temperatures, i.B. below 60 °

Main agreement with a Sals bond (as.B * -CON-), at higher temperatures (β · Β. over 80 °) mainly with amide, laid or amidine bonds (ie - C - V Jdar -cSS-) · In every case the process products are independent of the Watür and s on the ratios of the weave, useful for 9VT indtipfif ma lin Sweoke ale Zueätse au Iohlenwa # "" retofföltn.

164A9Q7

The saturated, alkyl-substituted succinic acid and its anhydrides are used with preference, since the products made from them are particularly effective additives for hydrocarbon oils. The succinic acid compounds are obtained by reacting maleic anhydride with a high molecular weight olefin or a chlorinated hydrocarbon as described above.For this purpose, the two reactants are heated to 100-2oo ° C, whereby an alkenylsuccinic acid anhydride is formed. The alkenyl group can be hydrogenated to an alkyl group. The anhydride can be hydrolyzed to the corresponding acid by treatment with water or steam. Both the anhydride and the acid can be converted into the acid halides or into esters, for example with phosphorus halides, phenols or alcohols. Instead of the olefins or the chlorinated hydrocarbons, other hydrocarbons with polar substituents which activate the reaction with maleic acid or its anhydride can also be used to prepare the succinic acid compounds. Such polar substituents are, for example, sulfide, disulfide, nitro, mercaptan, bromine, keto or aldehyde radicals. (

Examples of such hydrocarbons are polypropylene sulfide, di-isobutene sulfide, nitrated mineral oil, di-polyethylene sulfide, brominated polyethylene, etc. Another useful method for the production of succinic acids and their ÄTÜiydrides consists in the reaction of itaconic acid with a high molecular weight olefin or a polar substituted hydrocarbon - ' ⁰

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Acid halides of succinic acids can be produced by the reaction of the acids or their anhydrides with a halogenating agent such as phosphorus tribromide, biosphorus pentachloride or thionyl chloride. Uineetsung with an alcohol or phenol, such as methanol, ethanol, Qotadeoanol, cyclohexanol, Ihenol, naphthol, Oetylphenol etc. The esterification is usually t by an alkali such as Natriumbydroxyd or Hatriumalkyl & or catalyzed by an acid such as sulfuric acid · J> he alcoholic or phenolic fraction of the Beter evidently has only a small influence on their usefulness as a participant in the reaction in the manufacture of the end products *.

The upper limit of the useful amount of the nitrogen compound appears to be 2 moles per equivalent of amber. For education

of products with predominantly amidine bonds required * On the other hand, the lower limit is based on one-half equivalent of nitrogen compound per equivalent of Succinic acid compound on the stoichiometry for the Formation of products with predominantly imide or mixed Acyleaid bonds. In most cases it is preferred at least one equivalent of the nitrogen compound per Equivalent of acid compound used.

The following examples illustrate the manufacturing process the nitrogen-containing succinic acid compounds, the can be used according to the invention.

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example 1

A mixture of 1 equivalent of a duroh converting a «? chlorinated polybobutylene with maleic anhydride at 2oo ° C, polyisobutenylsuccinic acid anhydrides with an acid number of 98 and 1 equivalent of an aorolein-ammonia copolymer (pick-up ratio 1: 1) with a nitrogen content of 23 # is diluted with 40 # of its weight of mineral oil. ^{The mixture obtained is heated to 155 °} C. for 5 hours while blowing nitrogen through. The residue has a nitrogen content of $ 1.35.

A cyanoethyl ethylene amine is prepared by mixing 212 g of acrylonitrile with 216 g of an ethylene amine mixture, consisting of 75% triethylenetetramine and 25% diethylenetriamine, at tree temperature and heating for 5 hours at 11o - 13o ° C, finally at 3o mm ». To a mixture of 11 Io a Folyisobutenylbernsteinsäureanhydrids g acid number 113 (Ä'quivalentgewicht 5oo, molecular weight of the Polyieobutenylrestes about 85o) and 825 g of mineral oil are at 6o ° C to 143 g ^de e cyanoethyl-äthylenamins (nitrogen content. 31 # 8} 6} The mixture is heated to 150 ° -16 ° C. for 5 hours while nitrogen is passed through. * 6 ml of water are obtained as a distillate.

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Example 3

To a mixture of 43o g of the polyhydric acid anhydride of Example 2 and 355 g of SiaeralSl are added iodine at 60 ° -80 ° C. in one hour. The mixture is heated to -150-155 ° © for 5 hours. The residue has a nitrogen content of 2 _V 3 | £ «

Example 4

Into a mixture of Tooo g of the polyisobutenylber-succinic anhydride dee Example 2 and 500 g Äinerelcfl at 15o - 16o ° C below its surface an aur Sufficient amount of ammonia in one hour® The mixture is diluted with 169 g of mineral oil *, to 15 ° C heated and filtered. The piltrate has a nitrogen content from o, 77 #.

Example 5

A mixture of 417 g of Polyisobutenylberüsteiasäiireanhydrida of Example Z ₉ 3o g N- (g-Amlnotftityl) ~ triaietbylen ~ difijnin and 293 8 mineral oil is under Durchirlaeen Ross nitrogen in 5 hours at 6o-8o ° C produced · Bsr Hekstand has a nitrogen content of 1

Example 6 A mixture of 43o g of the Polyisobutnylbarasteicelure-

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anhydride of Example 2, 64 g 1,1- (dime thylaminoäthyl) -4-methyl-piperazine and 324 grams of mineral oil is prepared at 6O ⁰ O and then by bubbling with nitrogen at 15 ° - 155 ⁰ C heated. The BÜekstand has a nitrogen content of 1

Example 7

A mixture of 416 grams of the polyisobutenyl succinic anhydride of Examples 2, 124 g of N-Ihenylpiperazin and 356 grams of mineral oil is prepared at 6o ° C and then while blowing with nitrogen for 5 hours at 15 ° - 155 ⁰ C heated. This does not remove water. The residue has a nitrogen content of $ 2.07.

Example 8

A mixture of 11 10 g of the polyisobutenyl succinic anhydride from Example 2, 105 g of anthranilic acid and 884 g of mineral oil is heated to 100 ° C. for 2 hours. Dia mixture is cooled and ässm at 60-80 ⁰ C to 82 g of a mixture of 759 ^ Triäthylent β tramin and trains 25 $ diethylenetriamine "enter · The mixture thus obtained is by bubbling with nitrogen for 5 hours at 15ο - heated 155 ⁰ C. The residue has a nitrogen content of 1 _ton 72 pounds.

Example 9 A mixture of 45 g of di- (polypropoxy) coconut amine with a

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Holgewicht of 2265, 22 g of Pölyisobutenylbemsteinsäureanliydrias dee Example 2 and 44 g of mineral oil is 7 hours to 15 ° - 155 ⁰ O heated. The residue has a nitrogen content of 0.25 ^

Example 1o

A mixture of tooo g of the polyisobutenyl succinic acid hydride of Example 2, 159 g of menthandiamine and 500 g of mineral oil is produced at 70 - 100 ° C and below Blowing nitrogen through heated to 15o - 19o ° C until no more water distilliort .. The residue is with 258 g mineral oil diluted · The. Solution has a nitrogen content of $ 1.32.

Example ti

A mixture of 2o6g Ν, Ν'-di-sec.butyl-p-phenylenediamine, 1ooo g of the polyisobutenyibsuccinic anhydride from Example 2 and 5oo g of mineral oil is produced at 85 ⁰ C and heated to 150-2oo ° C for 5 hours. Then it is diluted with 29o g mineral oil, heated to 160 ° C and filtered. The Piltrat Mt © inen nitrogen content of 1

1q © ö to the Polyioobutenylbernsteinsäureanhydrid8 of B @ @ l @ 1 ISPI IAAD 5oo g of mineral oil g at 7o - 8o C ^G

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17.6 g of hydrazine added. «The reaction is exothermic. The mixture is heated to 150 ° C. for 1 hour, during which 9 g of water are precipitated as distillate. 40 g of iner Hthylenamin-Mieohimg the Zueaaawtßetsung of the Tetraätfkärlenpentainins at 70 ° - 80 ° C are then added to the residue. The mixture is then heated to 150-16o ° C. while blowing nitrogen through it until no more water distills off. The residue is diluted with 2oo g mineral oil, mt 16O ⁰ C. and filtered. The filtrate has a nitrogen content of $ 1.16.

Example 13

♦ -

To a solution of 1ooo g of Folyisobutenylbernstein-. Acid anhydride from Example 2 in 500 g of mineral oil is added at 50 ° -60 ° C. 28 g of 1,1-pumice-methyl hydrazine. The lÜBohung is 3 hours to 6o - heated 95 ⁰ C and then with 4o g of an ethylene amine mixture of ZusassBensetsung of ietraäthylenpentamine at 85 - 95 ⁰ C heated · The Misohung is 6 hours at 15o - erhitst 185 ⁰ C, wherein Ug water as Incurred distillate. The residue is diluted with 197 g of mineral oil, heated to 160 ° C. and filtered. The filtrate has a nitrogen content of $ 1.53.

Example 14

A sweetening of 1ooo g of the polyisobutenylbem @ t @ in8äureanhydride de "Example 2, 333 g 1,2-DiO-a ^ imcjpropoxy) -

Ethane and 500 g of mineral oil are heated to 14o - 17o ° C for 5 hours, 18 g of water being obtained as distillate. The liquid is diluted with 38o g of mineral oil , heated to 160 ° and filtered. The filtrate has 9taea nitrogen content of 2.2>f>.

Example 15

A mixture of looo g of Folyisobutenylbernsteinsäure "anhydride of Example 2, 416 g of di (3-amin @ propoxy) ~ ethyl ether and 5oo g of mineral oil is heated to ⁰ C 4 votes -1To 15o, in this case fall to 17 g of water as distillate. The Rüoketand is diluted with 433 g of mineral oil, ^{heated to 16G 0} O and filtered. The filtrate has a nitrogen content of 2.18 #.

Beiapial 16

A mixture of 1ooo g of the Polyieobutenylbarnsteinsänreanhydrids of Example 2, 36o g of a technical, primary tert-alkylamines _for its tert. Aüiyl-Eest contains 12 carbon atoms, and 500 g of mineral oil is heated to 155-25o ° C for 13 hours while blowing nitrogen through it. The residue is then heated to 150 ° C./1 mm, diluted with 337 g of mineral oil, heated to 160 ° C. and filtered. The filtrate has a nitrogen content of $ 0.87.

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Example 17

A mix of. 1ooo g of Polyieobutenylbemsteinsaureanhydrids of Example 2, 254 g Aminoguaniöiiifeügsrbonat and 5Co grams of mineral oil is prepared at ⁰ Thus G and S hours at 13o - heated 165 ⁰ C. The Hfickstand is mixed with 223 g of mineral oil, heated to 150 ° C and filtered «The Piltrat has a nitrogen content of $ 3.38 *

Example 18

A mixture of 1,000 g of the polyisobutenylsuccinic anhydride des.Bebeispiel 2, 178 g of 2-aminopyridine and 5oo g of mineral oil is blown with nitrogen

Heated to 14o - 175 ° C for 10 hours. Here, 16 g of water are obtained as de-distillate. The residue is diluted with 273 g of mineral oil and filtered. The filtrate has a @ a nitrogen content of $ 2.55.

Example 19

A mixture of 1 g of the polyisobutenylsuccinic anhydride from Example 2, 1o3 g of 2,6-diaibinopyridine and 500 g of mineral oil is blown with nitrogen

Heated to 130 ° C for 11 hours. Here 16 g fall Water as a distillate. The residue is with 223 g Diluted mineral oil, heated to 150 ° C and filtered. That Pil tr at has a nitrogen content of $ 2.15.

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Example 2o

A mixture of Ίοοο g of the polyisobutenylsuccinic anhydride from Example 2, 159 g of cyanguanidine and 233 g of toluene is boiled for 14 hours under RUokfluss, 7.15 g of water being removed by azeotropic distillation. The mixture is diluted with 74o g of mineral oil and heated to 150 ° C to remove the toluene. The residue is filtered. The piltrat has a nitrogen content of

Example 21

A mixture of 1632 g of the polyisobutenyl succinic acid anhydrides of Example 2, 2o7 g of a condensation product of acrolein and ammonia (molar ratio 1: 1) with a nitrogen content of $ 2o, 6o4 g of mineral oil and 175o g of toluene is refluxed for 3 hours. Here 31g of water are obtained as a distillate. By. Heating up The toluene is removed at 150 ° C./2o mm. The residue has a nitrogen content of £ 1.89.

Example 22

A nitrogen compound is made by mixing 100 g Cyanguanidine with 500 g of an ethylene amine mixture Composition of tetraethylene pentamine, 3 hour Heat to 7o - 8o ° C until the mass is homogeneous, and

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Filtration established. A mixture of tooo g of the eolyisobutenylbernetinic anhydride from Example 2, 96 g of the above filtrate and 164 g of toluene is refluxed for 10 hours. By heating to 15O ⁰ O / 2o mm, the toluene is then removed. The residue is diluted with 400 g of mineral oil and filtered. The piltrate has a nitrogen content of 3.43 #.

Example 23 \ '

To a mixture of 544 g of the acid anhydride-Polyisobutenylbernstein of Example 45 are added at ⁰ C 3o g urea 2> 233 g of mineral oil and 281 g of toluene. This mixture is heated to 130-135 ° C. for 11 hours, 2.5 ml of water being obtained as distillate. The residue is then heated to 140 ° C./2o mm and filtered. The filtrate has a nitrogen content of $ 1.

Example 24

A mixture of 1000 g of the polyisobutenylsuccinic anhydride from Example 2, 174 g of phenyl biguanide and 270 g of toluene is refluxed for 6.5 hours, 25 g of water being obtained as a distillate. The residue is diluted with 500 g of mineral oil and diluted to remove the toluene Heated 16o ° c / 2o mm. The residue is diluted with a further 265 g of mineral oil, heated to 150 ° and filtered. The Piltrat has a nitrogen content of 3

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Example 25

Please mix 92o g of the polyisobutenylsuccinic anhydride from Example 2 and 249 g of bis (dimethylaminopropyl) amine is refluxed until no more water is distilled off. The residue has a nitrogen content of 4%.

Example 26

A mixture of 1000 g of the polyisobtttenylsuccinic anhydride from Example 2, 363 δ aminopropyl octadeoylamine and 1314 g of mineral oil is heated to 200 ° C. for 24 hours. The residue is filtered »The piltrate has a nitrogen content of 1 _t o2 £»

Example 27

Bine mixture of 1ooo g of the polyisobutenylsuccinic anhydride of Example 2 and 258 g of di-n-butylamine is then heated for 12 hours 185 ⁰ C and 2oo ° 0/25 mm. The residue is diluted with 1157 g of mineral oil and filtered. The filtrate has a nitrogen content of O ₁ 8 $,

Example 28

A mixture of 297 g of the polyisobutenyl succinic anhydride of Example 2, 25 g of melamine and 2oo g of mineral oil is 9 hours at 19o - 25o ° C and then 7 hours

29o - 295 ⁰ C heated. The residue is mixed with 50 g of water, refluxed for 7 hours, dried and filtered. The filtrate has a nitrogen content of 2 #.

Example 29

A mixture of too g of the polyisobutenylsuccinic anhydride from Example 2 and 67 g of mineral oil is heated to 50.degree. To this mixture will be 59 g of a 855 ^ aqueous solution of hydrazine hydrate added · The mixture is 1.25 hours to I00 - heated 110 ⁰ G, diluted with toluene and long erhitat on 1o7 ° C * until no more water distilled off!. Then the toluene is distilled off. The residue has a nitrogen content of 0.8 #.

Example 3o

A mixture of 1, o equivalent of the dimethyl ester of ' Folyisobutenylsuccinic anhydride of Example 2 and 1, o equivalent of N, N-dibutyl-thiourea is in the Dissolved 5 times the volume of xylene. The mixture obtained is refluxed until no more water distills off azeotropically. Then the xylene is distilled off.

Example 31

Sin product is made

1 equivalent of polyisobutenyl succinic anhydride from Example 2

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prepared with 1 equivalent of pyrrolidine in 16O g of toluene at ⁰ C Thus, heated to 15o ° C for Toluolentfernung and the residue diluted with 35ο g of mineral oil.

Example 32

A product is made according to the procedure of Example 31 prepared, with 1 equivalent of hexahydro-1,3 »5-triazine is used in place of the pyrrolidine.

Example 33

A product is prepared according to the procedure of Example 31 produced, where 1. equivalent 1,3,4-dithiazolidine part of the pyrrolidine is used.

Example 34.

A product is prepared according to the procedure of Example 31 made using 2 equivalents of hexamethylenediamine be used instead of the pyrrolidine «

Example 35

An equimolar mixture of the polyisobutenyl succinic anhydride of Example 2 and N-octyl-thiourea diluted with the same volume of xylene. The mixture is refluxed for 30 hours. The backlog is one xylene solution of the product. .

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Example 36

A product is prepared according to the procedure of Example 35 made using oleic acid amide instead of the thiourine substance.

Example 37

A product is made following the procedure of the example prepared using 1,3-diphenylguanidine instead of the Thiourea is used.

•. ■ I

Example 38

A product is made following the procedure of the example produced using octadecaraidin instead of the thiourea β.

Example 39 A product is made according to the procedure of the examples

using guanylurea instead of thiourea (j

Substance is used « Example 4o

To a mixture of 396 g of the polyisobutenyl amber anhydride from Example 2 and 282 g of mineral oil are added 34 g of N-methyl-trimethylenediauin B in one hour at 60.degree. The Kisohung is 5 hours at 15 ° - 155 ⁰ C

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blown out with nitrogen. The residue has a nitrogen content of $ 1.41.

Example 41

A mixture of 3o8gMineralöl, 4oo g of the polyisobutenylsuccinic anhydride of Example 2 and 7ο g N- (2-ethylhexyl) -trimethylenediamine is prepared at 6o ° C and under bubbling of nitrogen for 5 hours at 15 ° - 155 ⁰ C heated. The residue has a nitrogen content of 1.4 #.

Example 42

A mixture of 386 grams of mineral oil, 528 g of PolyisobutenylbemsteineäureanhydridB of Example 2 and 59 g of N- (2-Hydroxyä ^ hyl) trimethylenediamine is prepared at 6o ° C and under bubbling of nitrogen for 5 hours at 15 ° - 155 ⁰ C heated. The residue has a nitrogen content of 1.56%,

BJ & apiel 43

A mixture of 185 g of mineral oil, 33o g of the PolyieobutenylberneteinsäureanhydridB of Example 2 and 88.5 g of t ^ 4-Bie (2-hydroxypropyl) -2-methylpiperazine is prepared at 60 ° C and 14.5 hours at 1So - 276 ⁰ C / 4o am heated * The residue has a nitrogen content of 1,

Example 44 To a mixture of 314 g mineral oil and 43o g des

1 09 8 OB / .1 β TO

- 27-16AA907

Polyisobutenylbernsteihsäureanhydrids of Example 2 at 60 ⁰ C 49 ~ {2-gt Hydroxyathyl) piperazine was added. The M β Chung- is heated to 150 ° C. for 5 hours while blowing nitrogen through it. The residue has a nitrogen content of $ 1.38. .

Example 45

A mixture of 382 grams of mineral oil, 528 g of polyisobutene ^ - succinic anhydride of Example 2 and 53 g 1-methyl-4- (3-aminopropyl) piperazine is prepared at 60 ⁰ C and under bubbling of nitrogen for 5 hours at 15 ° - 155 ⁰ C heated. The residue has a nitrogen content of $ 1.57.

Example 46

To a mixture of 800 g of the polyisobutenylsuccinic anhydride from Example 1 and 175 g of toluene, 77 g of a commercial mixture of alkylene amines and hydroxyalkyl-alkylene amines are added, consisting of about 2 $ diethylenetriamine, 36 ^ 1- (2-aminoethyl) piperazine, 11 £ 1 - (2-Hydroxyethyl) piperazine, 11 ^ H- (2-Hydroxy & thyl) ethylenediamine and 40? G higher homologues, which are formed by condensation of the amines mentioned. This mixture is refluxed for 16.5 hours, 12 ml of water being obtained as a distillate. The residue is then heated to 16o ° C./2o and diluted with 57o g of mineral oil. The end product has a nitrogen content of £ 1.57 *

109808/1670

Example 47

Sin product is naoh. the procedures of example 46 produced, with an equimolar Miechimg from ioBoniak and Bie (2-hydroxy-ethyl) amine instead of those mentioned there Amin-Hohung is used

Example 48

A product is made following the procedure of Example 46 produced using eneidin instead of the amine mixture mentioned there.

109808/167 ©

Claims (1)

Claim Lubricating oil containing substances substituted in kohlenwaaeeretoffe Succinic acid derivative of a nitrogenous compound, daduroh characterized in that it contains a succinic acid amide, amidine, imide or ammonium salt, which is also a succinic acid derivative of the general formula R-OH-O-X ² V wherein R is a hydrocarbon radical having at least 50 aliphatic carbon atoms and X is a halogen atom Hydroxy, alkoxy or acyloxy radical means, by reaction with ammonia, an aliphatic amine, an aromatic, heterocyclic or carbocyclic amine or polyamine or their hydroxy-substituted derivatives, a hydroxyalkyl-substituted alkylene amine, a urea, thiourea, hydra in, guanidine, amidine, amide, thioamide or cyanamide has been produced. Till