DE2229943A1 - OIL-SOLUBLE, ASH-FREE DISPERSING AGENT AND MINERAL LUBRICATING OIL FORMULATION, IN PARTICULAR FOR COMBUSTION POWER MACHINES - Google Patents

Description

Patent assessor Hamburg, the Ή. June 1972

German Texaco AG

2000 Hamburg 76 T 72 055 D

Sextuple gate 2

TEXACO DEVELOPMENT CORPORATION

155 East 42nd Street New York, N.T. 10017

UNITED STATES.

Oil-soluble, ash-free dispersant as well as Mineral lubricating oil formulation containing the same, in particular for internal combustion engines

The invention relates to an oil-soluble, ashless dispersant as well as a mineral lubricating oil formulation, in particular for ■ combustion engines.

Mineral lubricating oils alone can meet the demands made on the lubricating oil by modern internal combustion engines not meet; it is therefore customary to add, among other things, additives or additives to the base oil that improve the dispersing, Improve the cleaning, corrosion protection and wear-reducing properties of the lubricating oil formulation. the Formulation of a satisfactory engine lubricating oil is made difficult by the fact that engine oils have a wide range of Are subject to operating conditions. It is extremely difficult To formulate an engine oil in such a way that it can be used both at high speeds and at high speeds in city traffic

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(stop and go conditions) effective in case of low temples is. The formulation problem becomes even more difficult to solve when the lubricating oil is used in different types of engines, for example Diesel and Otto engines should be used because both have very high, but largely different, requirements put the lubricating oil.

US Pat. No. 3,275,554 already specified lubricating oils for internal combustion engines known to contain polyamines substituted with polyolefins as detergent additives.

The invention relates to an oil-soluble, ash-free dispersant, characterized in that that it is made from polybutenylalkylenepolyaminoalkanol with the following general formula:

XY
II
BN- (E '- N) - (E "- O) - H

^χ y

consists, in which X and Y are each H, (E "-0) H or E represent and E is a polybutenyl Best having a molecular weight of about 400 to 30,000; E ¹ is a divalent hydrocarbon radical with 2-8 carbon atoms, E" is a divalent hydrocarbon radical having 2-4 carbon atoms and χ has a value of 1-6 and y has a value of 1-5.

The invention also relates to a mineral lubricating oil formulation, especially for internal combustion engines, characterized by a proportion of about 0.1-10% by weight of the dispersant.

The polybutenyl-alkylenepolyaminoalkanol according to the invention can be divided in a two-stage reaction by adding

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next a polybutenyl polymer with an alkylene polyamine and the intermediate product obtained is reacted with an alkylene oxide in a second stage.

The polybutenyl starting material for this reaction is a Polymer of isobutene and can be prepared by "known polymerization processes. The polymer has an average molecular weight of about 400-50,000. Preferred is a polybutenyl polymer with an average. Molecular weight of about 700 - 3,000.

As alkylene polyamine starting compounds can ^- it is straight or branched diamine or polyalkylene polyamine or mixtures thereof use. Examples of suitable diamines are: ethylene diamine, propylene diamine, 1,4-butane and 1,4-pentane as well as 1,6-hexanediamine. Examples of suitable polyamines are: diethylenetriamine, pipe3? Azin, triethylenetetramine, N-aminoethylpiperazine, teträthylenpentamin and pentaethylene hexaraine.

A method for reacting the polybutenyl polymer with the alkylene polyamine is that first a halogen, for example chlorine or bromine derivative of polybutenyl polymer is prepared by one of the processes known for this purpose. In general, 1-2 moles of the polyamine are reacted with the halogenated polymer. This implementation is preferred carried out in the presence of alkaline compounds, however, the presence of alkaline compounds or solvents unnecessary. The reaction is generally carried out at temperatures of about 120-210.degree.

The intermediate product is then reacted with alkylene oxide and results in the dispersants according to the invention. Suitable alkylene oxides are: ethylene, propylene and butylene oxide, however, higher alkylene oxides and alkyl

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use substituted alkylene oxides. This reaction is generally carried out by dissolving the intermediate in a hydrocarbon solvent and slowly adding the alkylene oxide. This reaction can be done at room temperature or at higher or lower temperatures. The ratio of alkylene oxide to Pol.yamin can be found in the Modify manner that one completely ^ or partial alkoxylation of primary and secondary amines or spuch polyalkoxylation receives. The reaction mixture is then filtered and the solvent is evaporated therefrom in vacuo.

The dispersant obtained as the product of the above reaction corresponds to the general formula:

X Y

R .. N - (R ¹ - N) - (R "- O) - H

χ y

, in which X and Y each represent H, (R "-0) H or R and R a hydrocarbon residue with 25 - 5500 carbon atoms, R ' a divalent hydrocarbon radical with 2-8 carbon atoms, R "is a divalent hydrocarbon radical with 2-4 Is carbon atoms and χ has a value of 1-6 and y has a value of 1-5.

Compounds in which R is a polyisobutenyl radical with about 50-200 carbon atoms and y = 1 are preferred. Examples of suitable additives are polyisobutenyl (Cq ₀ ) tetraethylene pentaminoethanol, polyisobutenyl (C, - ^) - tetraethylene pentaminopropanol, polyisobutenyl (Cqq) - tetraethylene pentaminopolypropanol, polyisobutenyl (Cq ₀ ) -diethylenetriaminoethanol and polyisobutenyl (Cq 0) -diäthylenetriaminoethanol and polyisobutenyl (Cq 0) -diethylenetriaminoethanol (C-0) -diethylenetriaminoethanol.

That for the preparation of the lubricating oil formulation according to the invention The base oil used can be a paraffin-based,

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Naphthenic or paraffin / naphthenic mixed-base mineral oil distillate or residual oil. Paraffin-based lubricating oil distillate fractions are preferred for formulating the highest quality machine or engine lubricating oils. The base oils will generally have to be pretreated by solvent refining in order to improve their lubricity and viscosity / temperature behavior, and by dewaxing in order to remove paraffin components from the lubricating oil and to improve its pour point. For the formulation of the lubricating oils according to the invention, base oils with an SUS viscosity of about 50,000, preferably about 70-300 at 37 ₅ 8 ° G can generally be used. Mixtures of such base oils can also be used to create a base oil suitable for the production of single or multigrade oils.

In the following examples, the preparation of the invention Dispersants are explained in more detail:

Example 1:

4620 g of chlorinated polybutene with a molecular weight of about 1300 and a chlorine content of 2.76 % were mixed with 500 g (4.3 mol) of hexamethylenediamine and 191 g (1 »8 mol) of sodium carbonate. The reaction mixture was cooled, diluted with 4 l of hexane and filtered, and the piltrate was extracted with methanol. The hexane layer left an intermediate product containing 0.8% N on evaporation in vacuo at about 93 ° C.

2340 g of this intermediate was dissolved in a mixture of 800 ml of toluene and 334 ml of isopropanol. To this solution, 232 g (4 mol) of propylene oxide were added dropwise over 30 minutes. The mixture was then refluxed for 4 hours, filtered and the solvents removed at about 93 ° C. in vacuo. The dispersant obtained contained 0.8 % N.

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The effectiveness of the dispersant according to the invention was tested in the “Caterpillar 1-H Diesel Engine Test”. That is an industry standard test that starts with a 1 Y 73 ~ A one-cylinder diesel engine carried out as a lubricating oil test machine as described in FTMS 791a-346 T. This test is used to check whether the lubricating oil complies with MIL-L-2104 B complies with the specified specification.

The test engine was run for 480 hours "at a speed of 1800 rpm, and a fuel supply of 1248 kcal / min. (4950 BTU / min). The drive part of the Test engine for sticking of the piston rings, deposits on pistons and piston rings as well as wear of pistons and liner.

Example 2:

The procedure of Example 1 was repeated with 2000 g of chlorinated polybutenes (chlorine content 2.76%), 209 g (1.6 mol)

Imino Jais ^ propylamine and 85 g (0.80 moles) sodium carbonate.

The intermediate contained 1.2% N.

117 g of this intermediate product were dissolved in 150 ml of hexane and placed in a reaction vessel together with 15.5 g (0.27 mol) of propylene oxide and refluxed for 7 hours. The reaction mixture was then filtered and the solvent was evaporated off at approx. 82 ° C. in vacuo. The dispersant obtained contained 0.97 % ^N *

Example 3s

Following the procedure of Example 1, 3500 g of a chlorinated polybutenes (with 2.76 % chlorine content), 632 g (2.7 mol) of pentaethylene hexamine and 140 g (1.3 mol) of sodium carbonate were obtained to an intermediate product which contained 2% Ή, implemented.

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1500 s of this intermediate product were reacted in 1000 ml of toluene and 550 ml of isopropanol with 200 g (3j4 mol) of propylene oxide to form a dispersant which contained 2%.

Example 4- .: "Caterpillar 1-H-Test"

(see C. Zerbe, Mineralöle, Part II, 2nd edition,

(1969), pp. 170-187)

The Test.herangezogene this lubricant was a fully formulated motor oil containing an alkaline detergent, a zinc dithiophosphate and a pour point lowering agent (pour point depressant) in a paraffinic mineral oil having a viscosity of 535 SUS at 37.8 ⁰ C. The detergent obtained according to Example 1 was added to this fully formulated base oil in such a proportion that the lubricating oil used in the test contained 0.028% Ή.

This lubricating oil formulation according to the invention was tested with the "Caterpillar 1-H-Test" in the full test duration of 480 hours. The inspection of the piston showed 5% TGi ¹ (TGF «complete clogging of the piston groove] and 100% light paint film on the piston skirt above the 1st ring groove; no deposits below it. These test results demonstrate the effectiveness of the dispersant in limiting carbon and paint film deposits in diesel engines.

The effectiveness of the dispersant according to the invention in motor oils was also investigated in Otto engines. The ^{J <} lubricating oil formulations were tested in the laboratory test bench test (Bench Sludge I and II), in which a distinction could be made between oils with different abilities to limit deposits under low load (light duty). These bench mud tests were a measure of the dispersant formulation's ability to retain debris. The measured numbers obtained indicated the height of the sediment layer at the end of the test. The smaller this measurement

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P,

Pay for the Bench Sludge Tests I and II - were all the greater was the dispersing effect of the lubricating oil formulation.

The base oil used was a paraffinic hydrocarbon oil having an SUS viscosity of 125 at 37.8 ⁰ C. It three lubricating oil formulations were tested, in addition to the dispersants of the invention also contained an alkaline detergent, zinc dithiophosphate, and a polymethacrylate pour point depressants enthielten.Das lubricating oil A, the Dispersant from Example 1, in such a proportion that the ready-to-use formulation had a nitrogen content of 0.028%. Lubricating Oil B contained the dispersant of Example 2 and had a nitrogen content of 0.036%. Lubricating oil C contained the dispersant from Example 3 and 0.081 % Ή. The (comparative) lubricating oil D did not contain any ashless dispersant.

The results of the bench sludge tests are summarized in Table I:

Table I.

A. Bench Sludge I. Bench Sludge II B. . (mm sediment J " (mm sediment) Lubricating oil C. 0.1 0.5 Lubricating oil D. 0.3 0.7 Lubricating oil 0.1 0.4. Lubricating oil 0.5 3.8

(without dispersant)

As these tests show, the dispersants and lubricating oil formulations are the invention is highly effective for limiting deposits in 4-stroke gasoline engines, the operational sequence of which from these tests is simulated.

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Claims (6)

O? 72 035 D claims: 1) Oil-soluble, ashless dispersant, thereby characterized in that it is made from polybutenylalkylenepolyaminoalkanol with the following general Formula: X Y I I R_ N - (R ¹ - N). - (R "- O) - H in which X and Y each represent H, (R "-0) -H or R and R is a polybutenyl radical with a molecular weight of about 400-50,000; R ^{1 is} a divalent hydrocarbon radical with 2-8 carbon atoms, R "is a divalent hydrocarbon radical having 2-4 carbon atoms and χ has a value of 1-6 and y has a value of 1-5. 2) dispersant according to claim 1, characterized in that g e mark ei chnet, .that R has a molecular weight of about 700-3000. 3) dispersant according to claim 2, characterized in that that R has a molecular weight of about 1300. 4) dispersant according to any one of claims 1-3, d a through characterized in that R 'is a hexylene radical and R "is a methyl-substituted ethylene radical. is. 209882/1174 5) dispersant according to any one of claims 1-4, characterized in that χ and y · have the value 1. 6) Mineral lubricating oil formulation, especially for internal combustion engines, characterized by a proportion of about 0.1-10% by weight of the dispersant according to one of claims 1-5 209882/1 174