DE1274776B - Lubricating oil - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

ClOm

German class: 23 c -1/01

Number: 1274 776

File number: P 12 74 776.1-43 (L 42737)

Filing date: August 17, 1962

Opening day: August 8, 1968

From the French patent specification 1,254,094 are reaction products of hydrocarbyl-substituted succinic acids or succinic anhydrides, which substituent has more than 50 carbon atoms, with Äthylenaminen, such as ethylenediamine, diethylenediamine, triethylenetetramine and tetraethylenepentamine, known to the formation as lubricant additives and in particular to reduce the sludge ¹ in internal combustion engines and crankcases, particularly at alternating high and low operating temperatures, and as dispersants in hydrocarbon-based lubricants.

It has been found that the reaction product according to the invention has an even better dispersing effect is achieved.

The lubricating oil according to the invention is characterized in that it is a reaction product an alkyl or alkenylsuccinic acid amide, amidine, imide or ammonium salt with at least 50 carbon atoms in the alkyl or alkenyl radical with a boron oxide, boron halide, boric acid, boric acid ester or their mixtures in an atomic ratio of 0.1 to 10 boron atoms per nitrogen atom of succinic acid amide, -amidines, -imides or -ammonium salt contains.

The compounds containing nitrogen and boron are, in addition to being used as a lubricating oil additive, for. B. as pesticides, Anti-rust agents for metals, anti-corrosive agents, extreme pressure agents, anti-wear agents and Cleaning agent usable.

The lubricating oils can be of synthetic, animal, vegetable or mineral origin.

The reaction product is added in amounts of 0.1 to 10 percent by weight.

There may be other additives in the lubricants such. B. additional cleaning agents of the ash-containing type, viscosity index improver, pour point depressant, antifoam agent, High-pressure additives and rust, oxidation and corrosion protection agents.

The alkyl or alkenyl radical with at least 50 carbon atoms can, for. B. by chlorine, bromine, Keto, ether, aldehyde and nitro groups up to about 10% of the weight of the hydrocarbon portion be substituted.

The hydrocarbon substituents originate mainly from high molecular weight saturated petroleum fractions and of saturated olefin polymers, especially those with 2 to 30 carbon atoms, ζ. B. from 1-monoolefins such as ethylene, propene,! -Butene, isobutene, 1-hexene, 1-octene, 2-methyl lubricating oil

Applicant:

The Lubrizol Corporation,

Cleveland, Ohio (V. St. A.)

Representative:

Dipl.-Ing. G. Coldewey, Dr. E. Young
and Dr. V. Vossius, patent attorneys,
8000 Munich 23, Siegesstr. 26th

Named as inventor:
William Monroe Le Suer,
Cleveland, Ohio (V. St. A.)

Claimed priority:

V. St. v. America of August 18, 1961 (132 305), April 6, 1962 (185 520)

1-heptene, 3-cyclohexyl-l-butene and 2-methyl-5-propyl-1-hexene, or from olefins in which the double bond is not terminal, such as 2-butene, 3-butene, 3-pentene and 4-octene.

These substituents can also consist of copolymers of the olefins mentioned with other copolymerizable ones olefinic substances such as aromatic, cyclic and polyolefins, ζ. Β. from copolymers of isobutene and styrene, isobutene and butadiene, propene and isoprene, ethylene and piperylene, isobutene and chloroprene, isobutene and p-methylstyrene, 1-hexene and 1,3-hexadiene, 1-octene and 1-hexene, 1-heptene and 1-pentene, 3-methyl-l-butene and 1-octene, 3,3-dimethyl-1-pentene and 1-hexene, isobutene and styrene and piperylene, etc. are derived.

The alkyl or alkenyl radical should be essentially aliphatic and saturated; i.e. it should at least 80%, preferably at least 95%, are derived from aliphatic monoolefins, and not more than 5% of the covalent C - C bonds should be olefinic. In most cases it will this proportion can even be less than 2%.

Specific examples of this are the copolymer of 95% isobutene and 5% styrene, the telomer of 98% isobutene with 1% piperylene and 1% chloroprene, the telomer of 95% isobutene with 2% 1-butene and 3% 1-hexene, the telomer of 60% isobutene with 20% 1-pentene and 20% 1-octene, the

809 589/434

Copolymers of 80% 1-hexene and 20% 1-heptene, the telomer of 90% isobutene with 2% cyclohexene and 8% propene, the copolymer of 80% ethylene and 20% propene, etc.

The substituent R can also be saturated, aliphatic Hydrocarbons, such as highly refined high molecular weight white oils or synthetic alkanes, derived from the hydrogenation of high molecular weight olefin polymers or other olefinic ones Substances with molecular weights of 750 to 100,000 can be obtained.

The nitrogen-containing group of succinic acid derivatives is derived from substances that carry through a rest

15th

-NH

Marked are. The two free valences of the nitrogen atoms are preferably due to hydrogen or saturated by amino or organic radicals via direct N - C bonds. To the connections with the nitrogen-containing group mainly include ammonia, aliphatic, aromatic, heterocyclic or carbocyclic amines. They can be primary, or secondary amines as well Be polyamines, such as alkylene amines, arylene amines, cyclic polyamines and hydroxy-substituted derivatives of them.

Individual amines of these types are methylamine, N-methylethylamine, N-methyl-octylamine, N-cyclohexyl-aniline, Dibutylamine, cyclohexylamine, aniline, di- (p-methylphenyl) -amine, dodecylamine, octadecylamine, o-phenylenediamine, N, N'-di-n-butyl-p-phenylenediamine, morpholine, piperazine, tetrahydropyrazine, Indole, hexahydro-l, 3,5-triazine, 1-H-1,2,4-triazole, melamine, bis- (p-aminophenyl) -methane, phenyl-methylenimine, Menthane diamine, cyclohexylamine, pyrrolidine, 3-amino-5,6-diphenyl-l, 2,4-triazine, ethanolamine, Diethanolamine, quinone diimine, 1,3-indanediimine, 2-octadecyl-imidazolidine, 2-phenyl-4-methylimidazolidine, Oxazolidine and 2-heptyl-oxazolidine.

The nitrogen-containing groups are preferably derived from polyamines, especially from alkylene amines, mostly the formula

HN (alkylene - N) _n H

45

in which 11 is an integer, preferably below 10, A is hydrogen or a hydrocarbon and the alkylene radical preferably has fewer than 8 carbon atoms, e.g. B. methylene amines, ethylene amines, propylene amines, butylene amines, pentylene amines, hexylene amines, heptylene amines, octylene amines, other polymethylene amines and also the cyclic amines and their higher homologues, such as piperazines and aminoalkyl-substituted piperazines. Specific examples are: ethylene-diamine, triethylenetetramine, propylene-diamine, decamethylene-diamine, octamethylene-dimain, di- (heptamethylene) -triamine, tripropylenetetramine. Tetraethylene pentamine, trimethylene diamine, pentaethylene hexamine, di- (trimethylene) -triamine, 2-heptyl-3- (2-aminopropyl) -imidazolidine, 4-methyl-imidazolidine, 1,3 - bis - (2 - aminoethyl) - imidazolidine, Pyrimidine. 1- (2-aminopropyl) piperazine. 1,4-bis (2-aminoethyl) piperazine and 2-methyl-1- (2-aminobutyl) piperazine. Ethylenamines are particularly useful. as described in "Encyclopedia of Chemical Technology" by Kirk and Othmer, Vol. 5, pp. 898 to 905, Interscience Publishers, New York (1950).

Alkylene amines 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) - ethylenediamine, N, N'-bis (2-hydroxyethyl) -ethylenediamine, 1 - (2-hydroxyethyl) -piperazine, Hydroxypropyl diethylenetriamine, 1,4-bis (2-hydroxypropyl) piperazine, di-hydroxypropyl - tetraethylene pentamine, N - (3 -hydroxypropyl) -tetramethylene diamine and 2-heptadecyl-1- (2-hydroxyethyl) -imidazolidine.

The nitrogen-containing groups can also be selected from ureas, thioureas, hydrazines, guanidines, Amidines, amides, thioamides, cyanamides originate. Examples of such compounds are hydrazine, phenylhydrazine, N, N'-diphenylhydrazine, octadecylhydrazine, benzoylhydrazine, urea, Thiourea, n-butylurea, stearic acid amide, oleic acid amide, guanidine, 1,3-diphenylguanidine, 1,2,3-tributylguanidine, benzamidine, octadecamidine, Ν, Ν'-dimethylstearamidine, cyanamide, dicyandiamide, guanylurea, aminoguanidine.

The bond of a nitrogen atom to a succinic acid residue results in an amide or imide structure, those attached to a succinic acid imide residue have an amidine structure and those attached to a succinoyloxy residue Structure of a carboxylic acid ammonium salt.

The amino compound is expediently used in amounts of 2 moles up to 1 equivalent per equivalent of Succinic acid compound applied.

Boron oxides, boron oxide hydrates, BF ₃ , BBr ₃ , BCk, HBFj, boric and boronic acids (e.g. AIkVl-B (OH) ₂ or aryl-B (OH> ₂ , H ₃ BO ₃ , H2B4O7 The use of complexes of a boron trihalide with ethers, organic and inorganic acids, hydrocarbons, alcohols or phenols is a common method of introducing boron into the reaction mixture. Such known complexes are, for example, BFg- Diethyl ether, BF ₃ -phenol, BFs-phosphoric acid, BCL-j-chloroacetic acid, BBr ₃ -dioxane and BFs-methylethyl ether.

Individual examples of boronic acids are methyl, phenyl, cyclohexyl, p-heptylphenyl and dodecylboronic acid.

The conversion of succinic acid amides, amidines, imides or ammonium salts with the boron compounds can be done by simply mixing the components at the desired temperature. The use of an inert solvent is possible and often desirable, especially when highly viscous or solid substances are used for the reaction will. The inert solvent can be a hydrocarbon such as benzene, toluene, naphtha, cyclohexane. η-hexane or mineral oil. The reaction temperature can be varied within wide limits but preferably between 50 and 250 C. In some cases it can be 25 "C or even less. The upper temperature limit is determined by the decomposition point of the respective reaction mixture given.

The reaction is usually complete in 0.5 to 6 hours. After that, the product can be in the solvent dissolved and the solution by centrifugation or filtering of any turbidity or

insoluble components are cleaned. Usually the product is reasonably clean, like this that further cleaning is not necessary.

Eg game A

To 600 g (1 N atom) of the reaction product of 1 equivalent of polyisobutenyl succinic anhydride (polyisobutenyl group having a molecular weight about 850, acid number of 113 [corresponding to an equivalent weight of 500]) and 1 equivalent of a commercially available Äthylenaminmischung the approximate composition of tetraethylenepentamine (5 hours at 150 ⁰ C. in mineral oil) with an N content of 1.5%, 45.5 g (0.5 B atom) BF ₃ etherate (1: 1) are added at 60 to 75 ° C. The mixture is heated to 103 ⁰ C and then to 110 ° C / 30 mm to remove all volatiles to. The residue has a nitrogen content of 1.44% and a boron content of 0.49%.

Example B.

A mixture of 62 g (1 B atom) of boric acid and 1645 g (2.35 N atoms) of the reaction product of 3880 g of polyisobutenylsuccinic anhydride, 376 g of a mixture of 75% triethylenetetramine and 25% diethylenediamine in 2785 g of mineral oil (N content 2 ^{, 55%) is heated to 150 °} C. for 6 hours in a nitrogen atmosphere. The mixture is then filtered. The filtrate has a nitrogen content of 1.94% and a boron content of 0.33%

Example C

A mixture of 344 g of boric acid oleyl ester and 1645 g of the reaction product used in Example B is ^{heated to 150 °} C. for 6 hours and then filtered.

Example D

A mixture of 344 g of boric acid and 1112G the reaction product of 1385 grams of polyisobutenyl succinic anhydride and 179 g of a mixture of 74%) of triethylenetetramine and 25%) of diethylenetriamine in 1,041 grams of mineral oil is heated and then filtered for 6 hours at 150 C ^c.

Example E.

A mixture of 57 g triisobutyl borate, 13 g Mineral oil and 1045 g of the reaction product of 1 equivalent of polyisobutenyl succinic anhydride and 1.5 equivalents of diethylenetriamine is heated to 150 to 160 ° C for 3 hours and then at 170 "C blown with nitrogen. It is then heated to 150 ° C./20 mm.

Example F

A mixture of 34 g of BF3 in 1400 g of the reaction product from 1 equivalent of polyisobutenylsuccinic anhydride and 1 equivalent of a commercially available ethylene amine mixture corresponding to the tetraethylene pentamine is heated to 70 for 3 hours Blown up to 80 C with nitrogen.

Example G

A mixture of 31 g boric acid and 1175 g des The reaction product used in Example E is heated to 150 ° C. for 3 hours and filtered.

Example H

A complex of H3PO4 with 3 moles of BF3 is added dropwise to a mixture of 1344 g of the reaction product used in Example E and 432 g of mineral oil. An exothermic reaction occurs. The mixture is heated to 80 to 90 ^° C. for 0.5 hours and mixed with 520 ml of benzene. The solution is washed successively with 500 ml of water, 500 ml of water, 4- 250 ml of isopropanol. The washed product is heated to 150 ° C./38 to 68 mm for 6 hours, cooled and filtered. The filtrate has a nitrogen content of 1.34% and a boron content of 0.1%.

Example I.

A mixture of 12 g of sulfur, 124 grams of boric acid and 1018 of the reaction product of 1 equivalent isobutenyl and 2 equivalents of a g corresponding to the commercial tetraethylene pentamine Äthylenaminmischung is heated for 3 hours at 150 ⁰ C and filtered.

Example J

In a modification of Example I, 38 g of thiourea are used in place of the sulfur.

Example K

A mixture of 55 g BFa etherate and 480 of the reaction product of 1 equivalent isobutenyl and 1.5 equivalents of a g corresponding to the commercial tetraethylene pentamine Äthylenaminmischung is 0.5 hours to 80 to 90 ⁰ C and then heated to 120 ° C / 30mm.

Example L

A mixture of 372 g of boric acid and 3111g of the reaction product used in Example I is heated for 3 hours at 150 ⁰ C and then filtered.

Example M

272 = 4 moles of BF3 are slowly added to a mixture of 1790 g of mineral oil and 5370 g (7.3 N atoms) of des reaction product used in Example E. The mixture is left with nitrogen for 0.5 hours blown.

Example N

A mixture of 124 g of boric acid and 556 g of the reaction product used in Example I is ^{heated to 150 °} C. for 3.5 hours and then filtered.

For example, game-O

A mixture of boric acid and the reaction product of 6000 g of polyisobutenyl succinic anhydride (Acid number 24, molecular weight of the substituent about 50,000) and 108g of a tetraethylene pentamine corresponding commercially available ethylene amine mixture (1 B atom per N atom) is diluted with twice the volume of xylene for 3 hours heated to 150 ° C and filtered. The xylene is at 150 C / 0.25mm distilled off.

40

65

Example P

A mixture of boric acid and the reaction product of 544 g of polyisobutenyl succinic anhydride and 30 g of urea in 283 g of mineral oil and

281 g of toluene (1 B atom per N atom) is ^{heated to 150 °} C. for 3 hours and filtered.

Example Q

A mixture of boric acid and the reaction product of 1000 g of polyisobutenylsuccinic anhydride and 149 g of cyanguanidine in 233 g of toluene and 740 g of mineral oil (1 B atom per N atom) is ^{heated to 150 °} C. for 3 hours and filtered.

Example R

A mixture of BF3 etherate and polyisobutenyl succinimide (molecular weight of the polyisobutenyl radical 1000) (1 B atom per N atom) is ^{heated to 150 °} C. for 3 hours and filtered at this temperature.

Example p

A mixture of boric acid and the reaction product of 1000 g of polyisobutenylsuccinic anhydride and 360 g of a technical tertiary alkylamine with 12 to 14 carbon atoms in the alkyl radical in 500 g of mineral oil (1 B atom per N atom) is heated to 150 ^° C. for 3 hours heated and filtered.

Example T

A mixture of boric acid and the reaction product of 430 g of polyisobutenylsuccinic anhydride and 64 g of l- (dimethylaminoethyl) -4-methylpiperazine in 324 g of mineral oil (1 B atom per N atom) is ^{heated to 150 °} C. for 3 hours and filtered.

Example U

A slurry of 409 g of boric acid in 740 g of mineral oil is heated to 140 ⁰ C. To this slurry an oil solution of the reaction product used in Example I is added in 3.5 hours at 130 to 140 ⁰ C. The mixture is blown with nitrogen at 150 to 158 ° C. for 7 hours. The product is then mixed with diatomaceous earth and filtered. After 2.2 hours of filtration, the product is obtained in a 96% yield. It has a boron content of 1.89% and a nitrogen content of 2.47%.

The effectiveness of the claimed reaction product is evident from the results of an inhibition cleaning test, in which a 350 ml sample of a lubricant containing 0.001% iron naphthenate and 1.5% of the additive to be tested was placed in a borosilicate tube of 5 for 48 hours ■ 38 cm to 149 ⁰ C is heated. A clean lead copper bearing is dipped in the lubricant along with an SAE 1020 steel test pad. The lubricant blows 101 air per hour. The oxidized sample is cooled to 5O ⁰ C, after which 0.5 percent by volume of water are dispersed in the sample. The sample is left to stand for 15 hours at room temperature and then filtered through a filter paper (double thickness) under slightly reduced pressure. The precipitate is washed with naphtha to constant weight and given in milligrams of sludge per 100 ml of oil. The bearing is washed with naphtha, dried and weighed. The change in weight is given in milligrams. The viscosity of the lubricant at 38 and 99 ⁰ C before and after the test is noted. The amount of silt is a criterion for the suitability of the additive to prevent the formation of undesired deposits; the change in weight of the bearing is a criterion for the corrosiveness of the lubricant, and the change in viscosity of the lubricant is an indication of its resistance to oxidation. The lubricant used in this test is a normally refined mid-continent mineral oil with a viscosity of about 200 SUS at 38 ° C.

Table I. '99 ⁰ C Weight change mud additive Viscosity increase 3.1% of the camp
mg (mg per 100 ml des
Lubricant) (1.5 percent by weight of solvent
free addition) 38 ° C > 10% -53.5 1145 No 13.2% 0.9% > -200 > 100 Alkenyl succinic acid amide according to
Example 17 of the French Pa
publication 1 254 094 and Reak
tion product from example B .. > 30% 2.8% -13.9 1.8 Product of example F 1.3% 2.1% +0.9 2.0 Product of example A 11.1% 4.1% + 3.3 2.4 Product of example K 8.9% 3.2% -1.6 18.7 Product of example N 11.2% -1.7 60 Example Q 'Product 15.2%

CRC-EX-3 engine test

The lubricant in the crankcase of a 1954 6-cylinder Chevrolet engine is tested for 144 hours under periodically recurring conditions. Each cycle consists of 2 hours with an engine speed of 500 ± 25 rpm under zero load and an oil sump temperature of 38 to 52 ° C and an air-fuel ratio of 10: 1; 2 hours at an engine speed of 2500 ± 25 rpm under the load of 40 brake horsepower and an oil sump temperature of 66 to 77 ⁰ C and an air-fuel ratio 16: 1 and 2 hours at an engine speed of 2500 ± 25 U / min under a load of 40 brake horsepower and an oil sump temperature of 116-121 ⁰ C and an air-fuel ratio of 16: 1st

At the end of the test, the engine is dismantled and examined for deposits. The lubricant is then rated firstly according to the extent to which the piston ring groove is filled, secondly according to the amount of sludge in the machine (on a scale from 80 to 0.80 means no sludge, 0 means a lot of sludge) and thirdly, after the total amount of deposits in the engine (Sludge + paint) (on a scale from 100 to 0, 100 means no deposits, 0 means extremely many deposits). The lubricant used in the test is a mineral lubricating oil SAE 20 containing 1.41% of the Example L product. The following result was obtained with this Lubricant obtained: piston ring groove fill 1%, sludge 75.3, total deposit 93.4.

Caterpillar CRC-Ll engine test

In this test, the lubricant in the crankcase of a 4-stroke diesel engine, which has a cylinder size of 14.6 x 20 cm and a compression ratio of 15: 1, is tested for 480 hours under the following conditions: speed 100 rpm; BTU inlet per minute 2900 to 3000; Load 20 brake horsepower; Water outlet temperature 79 to 82 ⁰ C and oil temperature 63 to 66 ⁰ C. The lubricant is rated firstly according to the cleanliness of the piston on a scale from 0 to 100 (100 means completely clean, 0 means a maximum of deposits) and secondly according to the ring groove filling. A lubricant made from a mineral oil SAE-IOW-30 with 2% of the product of Example L gave the following result in this test: piston ring groove filling 19%, piston cleanliness 96.0.

CRC-L-4-545 engine test

This test is carried out in a 6-cylinder gasoline engine for 36 hours under the following conditions: speed 3150 rpm; Load 30 brake horsepower; Cooling jacket outlet temperature 93 ° C; Inlet ^{temperature 88 0} C; oil sump temperature 130 ⁰ C; 14.5: 1 air-fuel ratio. Lubricant is rated based on the weight loss of the bearings, the cleanliness of the pistons, and the total build-up in the various parts of the engine. In this test, a lubricant made from a mineral oil SAE-10W-30 with 2% of the product of Example L gave the following results: piston cleanliness 9.5 (10 is perfectly clean); Total deposits 96.7 (100 is perfectly clean) and an approximate weight loss per bearing of 2.5 mg.

Test according to the US Army Ordinance Description AXS-1569 for testing axle lubricants

A Chevrolet car is placed on castors with its rear wheels. After a short break-in period (12 minutes at 40 km / hour in high gear) the machine runs with the throttle valve open accelerated to 64 km / hour. Then the throttle valve is completely closed, like this. that the speed drops to 16 km / hour. This cycle is repeated 4 times. The machine is now gradually accelerated in high gear to 96 km / hour and when this speed is reached accelerated further to 128 km / hour with the throttle valve wide open. Then the throttle valve is completely closed again, so that the speed drops to 96 km / hour. This acceleration and deceleration is repeated 10 times. The rear axle lubricant is then based on the appearance of the surfaces of the Gearbox rated on a scale from 1 to 5 (1 means no scratches, and 5 shows 100% Scratches). The lubricant used in the test is a mineral lubricating oil SAE 90 with the various accessories.

Table II

lubricant
Weight percent valuation Mineral oil SAE 90 + 0.9% zinc-di- (4-methyl- 2-pentyl) dithiophosphate 5 Mineral oil SAE 90 + 0.9% zinc-di- (4-methyl- 2-pentyl) dithiophosphate and 2.5% of the product of example L,, 1 Mineral oil SAE 90 + 3.5% of the product of the Example L 5

Anti-corrosion test

A lubricant made from 300 g of a mineral oil SAE 30 and the additives, in which a bearing piece (Copper-lead surface, 28 g), air is blown at 149 ° C with 28.3 l / hour. At the At the end of the test, the weight loss of the bearing piece is determined; the lower the loss, the more The lubricant is less corrosive.

Table III

Additive in the lubricant Loss of the Volume percentage Stock item
in mg 3.8% 4,4'-bis-methylene (2,6-di-tert-butylphenol) ..... 27 0.8% 4,4'-bis-methylene (2,6-di-tert-butylphenol) 26th 0.8% 4,4'-bis-methylene (2,6-di-tert-butylphenol) + 3% of the product of Example L. 4th 0.8% 4,4'-bis-methylene (2,6-di-tert-butylphenol) 4- 2% of the product of Example L 1 0.8% 4,4'-bis-methylene (2,6-di-tert-butylphenol) + 1% of the product of Example L. 0

Claims (1)

Claim: Lubricating oil containing a reaction product of an alkyl- or alkenyl-substituted succinic acid derivative, characterized in that it is a reaction product of a Alkyl- or alkenylsuccinic acid amide, -amidine, 809 519/434 Il 12 -imide or -ammonium salt with at least 'substance atom of succinic acid amide, amidine, Contains 50 carbon atoms in the alkyl or alkenyl radical with imides or ammonium salts. a boron oxide, boron halide, boric acid, boron acid esters or their mixtures in atomic proportions. ratio of about 0.1 to 10 boron atoms per stick- 5 French patent specification No. 1254 094. 809 589/434 7.68 © Bundesdruckerei Berlin