DE1260062B - Mineral lubricating oil - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN 4ZM ^ PATENT OFFICE Int. Cl .:

ClOm

EDITORIAL

German class: 23 c -1/01

Number: 1260 062

File number: E 22946IV c / 23 c

Filing date: May 25, 1962

Open date: February 1, 1968

The invention relates to mineral lubricating oils with a content of calcium-containing sludge inhibitors. the Oil additives consist of colloidal dispersions of calcium salts, mainly calcium carbonate, in the Mixture with phosphorus sulphurized hydrocarbons and alkylated phenols and / or alkylphenol sulphides.

Complex or colloidal dispersions of salts of polyvalent metals, especially of alkaline earth salts, which have a high ratio of metal to organic acidic constituents are than Sludge inhibitors suitable for crankcase lubricating oils. However, it has hitherto been difficult to obtain such dispersions with calcium salts that do not show any cloudiness.

Such lubricating oil additives were previously made by reacting alkaline earth oxides and / or -hydroxides with carbon dioxide in the presence of alkylphenols and phosphorus-sulphurized hydrocarbons won. The phosphorus sulphurized hydrocarbon serves to remove the constituents to be kept in colloidal dispersion. The stability largely depends on the fineness of the in particles located in the colloidal dispersion. This, in turn, can easily be determined by a how the finished product is very cloudy. A cloudiness of more than 100 nephelo in a mixture, which contains 5 percent by weight of additive in white oil is no longer permitted.

Even with the use of large amounts of surfactants, the more expensive the product, it does not succeed in clouding ^poor: bright additives with high metal content to win.

The invention now relates to a mineral lubricating oil which, in a known manner, is a reaction product from a phosphorus sulphurized hydrocarbon, an alkylphenol or alkylphenol sulfide, calcium hydroxide or contains calcium oxide and carbon dioxide. The new lubricating oil is characterized by that the reaction product in the presence of ammonium hydroxide or a mixture of ammonium hydroxide and ammonium sulfate or an amine having 1 to 4 carbon atoms in the molecule has been made.

The ratio of calcium equivalents to surfactant equivalents should be at least 3: 1; also equivalent ratios up to about 13: 1 are still possible.

The phosphorus-sulphurized hydrocarbons which can be used according to the invention are known and can be obtained by reacting a sulphide of phosphorus, e.g. B. P ₂ S ₅ , made with a hydrocarbon mineral lubricating oil

Applicant:

Esso Research and Engineering Company,

Elizabeth, N. J. (V. St. A.)

Representative:

Dr. K. Th. Hegel, patent attorney,

2000 Hamburg 50, Große Bergstr. 223

Named as inventor:

Joseph Versteeg, Roselle, N. J. (V. St. A.)

Claimed priority:

V. St. v. America June 30, 1961 (120 918)

will. Terpenes, such as pinene, heavy petroleum fractions, distillates or residues, are preferred contain less than 5% aromatics and have a viscosity of 140 to 250 SUS at 98.9 ° C, and Polyolefins with Staudinger molecular weights in the range from 500 to 200,000 and with 2 to 6 carbon atoms per monomer unit. Polybutenes with Staudinger molecular weights in the range of 700 to 100,000 are particularly preferred.

Preferably the phosphorus sulphurized hydrocarbon is made by reacting about 4 moles of the hydrocarbon (e.g. polyolefin) made with 1 mole of phosphorus pentasulfide.

The alkylphenol preferably has a molecular weight in the range of about 200 to 700. One can z. B. the product of the alkylation of phenol with diisobutylene or with tripropylene, d. H. Nonylphenol, use. Under certain circumstances it is also possible to replace the alkylphenol or part thereof with an alkylphenol sulfide to replace. Alkyl phenol sulfides are thioethers of alkyl phenols; H. Connections, at which the alkylated phenol groups are linked by a divalent sulfur atom. The alkylphenols can be converted into alkylphenol sulfides in a known manner by reaction with sulfur dichloride will.

The ammonium sulfonates used in the invention are ammonium salts of sulfonated Sulphonic acids obtained from natural or synthetic hydrocarbons. The preferred Sulphonic acids have molecular weights in the range of 300 to 700 (as soda soaps). The synthetic

709 747/506

Sulfonic acids preferably have molecular weights in the narrower range from 400 to 600. The acids can contain more than one sulfonyl group in the molecule. Suitable sulfonic acids are made by sulfonating alkyl aromatic hydrocarbons such as didodecylbenzene. You can also treat it by made from hydrocarbons in the lubricating oil sector with concentrated or fuming sulfuric acid as is known, the oil-soluble so-called "mahoganic acids" are formed.

The reaction product according to the invention is prepared as follows: First, a solution or a mixture of a phosphorus-sulphurized hydrocarbon, an alkylphenol and optionally an ammonium sulphonate in a hydrocarbon oil is produced. The hydrocarbon oil may contain any fraction whose boiling point is so high that the oil ₁ under the reaction conditions do not evaporate. Light fractions of lubricating oil are particularly suitable. Then the mixture is mixed with ammonium hydroxide, then with water and then with calcium oxide and / or calcium hydroxide. Finally, carbon dioxide is bubbled into the mixture for 2-3 hours. The reaction product is dehydrated and filtered. The broadest and preferred temperature ranges and treatment times for each of the process steps are shown in Table I.

Table I.

Procedural stage

Temperature range, ⁰ C far I preferred

1. Mixture of phosphorus sulphurized hydrocarbon, alkylphenol, optionally
Ammonium sulfonate and
Thinner oil

2. Addition of NH ₄ OH and
Stir (e.g. 10 minutes ; the time is not decisive)

3. Addition of water

4. Addition of dry
Ca (OH) ₂ and leave to act (e.g. 20 minutes;
however, the time is not
decisive)

5. Introduction of CO ₃

(2 to 6 hours, e.g.
3> hours)

6. Dehydrate through
at least 10 minutes
long heating

7. Filter

15 to 82

15 to 82 15 to 82

15 to 82 49 to 88

66 to 204 204 to 127

32 to 38

38 to 54 54

Table II

Phosphorus sulphurized
Hydrocarbon ..

Alkylated phenol

Ammonium sulfonate ...

Thinner oil

NH ₄ OH (29 ° / ₀ NH ₃ ) ..

water

Ca (OH) ₈ (or equivalent amount of CaO)

CO ₂

Weight percent

Furthest
area

17 to 25

5 to 20

0 to 5

25 to 60
0.2 to 20

0 to 5

3 to 20

2 to 11

Preferred area.

19 to 22

6 to 10
0.5 to 2

35 to 45

4 to 10
0 to 1.5

5 to 18
3 to 10

The amount of KobJendioxydmenga is preferably im Range from about 80; up to 95% of the theoretical Conversion of calcium into calcium carbonate required amount.

example 1

In this example, the equivalent ratio is calcium to surfactant about 3: 1.

A mixture of 536 g of mineral oil, 279 g of phosphorus sulphurized hydrocarbon and 112 g of nonylphenol is heated to 77 ° C. A slurry of 82.5 g of Ca (OH) ₃ in 100 g of water is then added over the course of 20 minutes, the temperature being maintained at 77.degree. _{25 liters of CO 2} (measured at 25 ° C.) are then passed into the mixture over the course of 80 minutes. Then the product is dehydrated and filtered.
The same procedure is repeated; in this case, however, 2 * 4 g of ammonium hydroxide (29% NH ₃ ) are added before the calcium hydroxide suspension is added. The improvement in turbidity and color achieved by the addition of ammonium hydroxide is shown in Table III.

Tabel UI With
ammonia Without
ammonia 18th
1
bright
3.8 45
Turbidity nephelo *
Color, ASTM
Color »appearance
Calcium, weight percent 47
1%
dark
3.9,

49 to 66 63 to 71

66 to 188 188 to 149

The proportions of the reactants can vary within the ranges given in Table II. Instead of ammonia, an aliphatic amine with 1 to 4 carbon atoms in the molecule can be used will. The amount of ammonia or amine must be sufficient to match the weight ratio of nitrogen to bring calcium to at least 0.02: 1.

* Measurement ia 5gewichtspre> zentiger concentration in white oil.

Example 2

Following the general procedure of Example 2, but using an equivalent ratio of calcium to surfactant of 3.5: 1 and replacing the ammonium hydroxide with tert-butylamine, an oil additive is prepared from the following ingredients:

Mineral oil 52Og

Phosphorus sulphurised polybutene 279 g

Ca (OH) _a 97g

Water 12Qg

Nonylphenol 110 g

CO ₂ 271

(measured at 25 ° Q tert, butylamine 6 g

The same manufacturing process is repeated without adding amine. The results can be found in Table IV. It can be seen that the values for the turbidity and the filter speed by the addition of the Amines can be greatly improved.

16.0 percent by weight from calcium hydroxide and 9.0 percent by weight from CO ₂ . The product has the composition given in Table V. The equivalent ratio of calcium to surfactant is about 8.5: 1.

Table IV

Manufacture of a sludge inhibitor

at an equivalent ratio of calcium

to surfactant of 3.5: 1

Nitrogenous 5.1 Respondents 52 none | tert-butylamine Calcium content of the product, 713 Weight percent 4.4 Turbidity, nephelo * 109 Filtration speed, l / h / m ² 36.7

* Measured in 5 weight percent concentration in white oil.

Example 3

A sludge inhibitor is prepared according to the preferred method outlined in Table I. The starting material consists of 19.8 percent by weight of the phosphorus sulphurized hydrocarbon prepared according to Example 1, 6.5 percent by weight of nonylphenol, 1.6 percent by weight of ammonium petroleum sulfonate with a molecular weight of about 450, and 41.7 percent by weight of a neutral mineral oil (viscosity 150 SUS at 37.8 ⁰ C) to 1.0 weight percent water, about 4.4 percent by weight of technical grade ammonium hydroxide (29% NH ₃₎ to

Table V

composition

of the product
Weight percent

Approx 9.0

CO ₃ 12.0

Phosphorus sulphurized

Hydrocarbon 22.5

Nonylphenol 7.4

Neutral mineral oil 47.4

Ammonium sulfonate 1.7

Example 4

The procedure is as in Example 4, but without the addition of ammonium sulfonate and with different equivalent ratios of CO ₂ to calcium. The results can be found in Table VI. Will the ammonia

As completely omitted, the product becomes unfilterable and therefore worthless, since the calcium carbonate is then not in colloidal form. In the tests in which ammonia but no ammonium sulfonate is added, the best results for turbidity, filter speed and odor are obtained with a chemical equivalent ratio of CO ₂ to calcium of less than 0.9. A better quality of the product is achieved if both ammonia and ammonium sulfonate are added.

Table VI

Nitrogenous
Respondents

Equivalent ratio CO ₂ : Ca in the initial material turbidity,
Nephelo **

Filtration speed

l / h / m ²

odor

Ammonium sulfonate and ammonia *

ammonia

Ammonia "...

ammonia

none

* Example 3.

0.94
0.99
0.94
0.89
0.89

40
125
114

87

204
40.8
40.8

72.5

cannot be filtered ** Measured in 5% by weight concentration in white oil.

weakly phenolic
strong H ₂ S odor
strong H ₂ S odor
weakly phenolic

Example 5

55

Following the general procedure of Example 2, but with an equivalent ratio of calcium to surface-active agent of about 4: 1, an additional concentrate of 397 g of a 68% concentrate of phosphorus-sulphurized polybutene in mineral oil, 112 g of nonylphenol, 110 g of Ca (OH) ₂ , HOg water, 418 g neutral mineral oil and 301 CO ₂ (measured at 25 ° C). The process is repeated with the same components and quantities, but with the addition of 61 g ammonium hydroxide (29% NH ₃ ). The values for the turbidity, measured as a 5% concentration of the respective products in white oil, and for the filtration rates are given in Table VII. It can be seen that with an equivalent ratio of caleium to surface-active. Mean of 4: 1 without ammonium hydroxide no satisfactory product is obtained.

Table VII

Influence of NH ₄ OH with an equivalent ratio of calcium to surfactant of 4: 1

Amount of NH ₄ OH Cloudiness, nephelo
(5% in white oil) Filter
speed
l / h / m * None
2.7% > 130
17th 200
1000

Example 6

Takelle VIII (continued)

To produce an oil additive with an equivalent ratio of calcium to surface-active agent in the order of about 8: 1, the second part of Example 5 is followed (ie using NH ₄ OH), but twice the amount of Ca (OH) ₂ , 1.6 times the amount of NH ₄ OH solution and 2.5 times the amount of CO ₂ . This initially results in a product with an unsatisfactory turbidity value (130 Nephelo). The process is repeated with the proviso that some of the nonylphenol and the NH ₄ OH are replaced by ammonium petroleum sulfonate with a molecular weight of 450. The reactants consist of 397 g of a 68 weight percent concentrate of phosphorus sulphurized polybutene in mineral oil, 91 g of nonylphenol, 220 g of Ca (OH) ₂ , HOg of water, 61g of NH ₄ OH (29% NH ₃ ), 418 g of neutral mineral oil, 41.7 g a 50% concentrate of ammonium petroleum sulfonate in mineral oil and 70.21 CO ₂ (measured at 25 ° C). This second product shows a turbidity value of 27 nephelo (in 5% concentration in white oil), while the first product, made without ammonium sulfonate, gives a value of 130.

Example 7

To the effect of an even further increase in the equivalent ratio of calcium to surface-active Investigating agents will have products with equivalent ratios of 8.3, 10.2, and 13.6 using the amounts of reactants given in Table VIII. The turbidity values and the filtration speeds when filtering the products are also shown in the table. Only the product with an equivalent ratio of 13.6: 1 is unsatisfactory.

Other research has shown that a product with a haze value of 36 Nephelo made at a calcium to surfactant equivalent ratio of 13.4: 1 can be done if the manufacture is done in two stages by going in the first stage with a Calcium to surfactant equivalent ratio of 8: 1 working, then dehydrated, the product is filtered and then more lime, carbon dioxide and ammonia are added.

Table VIII

Influence of increasing the calcium to surfactant equivalent ratio

Ammonium sulfonate, g
(50% concentrate,
Molecular weight 450).

CO ₂ ,! (Measured at 25 ⁰ C) ...
CaO, g

Filtration speed,
l / h / m ²

Turbidity value of the product,
Nephelo (5% concentration in white oil)

Equivalent ratio

8.3

31.2
50
124.8

147
38

10.2 13.6

40

64

156

114
91

31.2 82.5 204

<40.8> 130

Example 8

As the following experiments show, the total water content of the reaction mixture appears to be one Calcium to surfactant equivalent ratio of 8: 1 has some influence to have the nature of the product. Using the procedure for the second product of Example 7 manufacturing process described, d. H. with the addition of ammonium sulfonate, the total water content of the initial goods changed. The results, compiled in Table IX, show that in one Equivalent ratio of calcium to surfactant of 8: 1 of the total water content Reactants should be in the range of about 7.2 to 8.2 percent by weight, based on the reactants.

Table IX
Influence of the water content of the reaction mixture

Calcium
link Total water
salary * (% of
Starting goods) Turbidity,
No
phelo ** Filter
speed
l / h / m ³ CaO J
Ca (OH) ₂ ..
CaO 7.0
7.2
7.5
7.9
8.0
8.2
8.5
10.5 > 130
38
27
40
40
65
128
> 130 497
147
187.5
159
216
130.5
<40.8
408

* Added water + water in the Ca (OH) ₂ + water

in the NH ₄ OH solution (29% NH ₃ ).
** 5 ° / _o solution in white oil.

Conversion product of
Polybutene with P ₂ S ₅ , g
(68% concentrate)

Nonylphenol, g

Neutral solvent mineral oil, g

NH ₄ OH (28% NH ₃ ), g

Water, g

Equivalent ratio
8.3 I 10.2 I 13.6

55

300
67

312
46
42

300
67

312
46
80

300
67

312
46
80

Example 9

The sludge-inhibiting properties of one according to the invention with an equivalent ratio of Calcium to surfactant of 8: 1 oil additive made in a low temperature engine test investigated in which the running conditions of the engine are chosen so that frequent stopping and restarting are mimicked will. A six cylinder Ford engine gets 3.7851

of the oil to be investigated and a total of 286 hours below those given in Table X. Conditions are allowed to run with the trial periods repeated until the end of the test.

Table X Conditions in the low temperature engine test

10

period

Period 2

Period 3

Period duration, hours

Running speed, rev / min.
Air to fuel ratio ...

Braking horsepower load

Torque, mkg

oil sump temperature, ° C

Cooling water outlet temperature, ⁰ C.

1.5
500
11: 1
0
0

82.2 ± 2.6
87.8 + 2.8

2000

13.5 to 14: 1
40
14.5

82.2 ± 2.8
71.1 ± 2.8

2000

13.5 to 14: 1 40

14.5.

101.7 ± 2.8

82.2 ± 2.8

After the first 66 hours and every 44 hours thereafter, the engine is examined by the Oil pan, the rocker arm cover and the cover of the bumper chamber can be removed and the various parts including the oil filter, oil pan, crankshaft, bumper chamber, the cover of the bumper chamber, the rocker arm cover and the rocker arm system for sludge separation are evaluated, based on an error value system in which the number 0 a completely clean machine part and the number 10 one covered with the greatest possible amount of mud Machine part means.

The following oils are examined:

(1) Lubricating Oil A, composed of 98 percent by volume of a highly refined viscosity grade oil base SAE 30, 0.3 volume percent from a viscosity index improver, 0.7 volume percent from a zinc dialkyldithiophosphate

(with C ₄ - to C ₅ -alkyl groups) as a wear-reducing agent and 1 percent by volume from an additive concentrate prepared according to Example 4 and containing 8.6% calcium.

(2) Lubricating oil B, consisting of 96 percent by volume of the same oil base, 0.3 percent by volume the same viscosity index improver, 0.7 volume percent from the same zinc dialkyldithiophosphate like lubricating oil A and 3 percent by volume from a commercially available sludge inhibitor, the colloidal barium carbonate and stabilized with a phosphorus-sulphurized polybutene Contains phenolate. The latter sludge inhibitor contains 10.7 percent by weight BaO. The lubricating oils A and B are so composed that they are approximately equimolecular Contains concentrations of metal.

The test results can be found in Table XI.

Table XI
Results of the cryogenic sludge test

running time on 66 Total error value for sludge separation Lubricating oil B hours 110 Lube Oil A 154 0.14 198 0.06 0.32 ³⁵ 242 0.16 0.63 286 0.25 0.81 0.31 1.21 0.53 1.47 0.78

Any oils can be used as the oil base, e.g. B. those that are obtained from paraffinic, naphthenic, asphaltic or mixed base crude oils by appropriate refining methods. Synthetic lubricating oils of suitable viscosity can also be used, e.g. B. Sebacic acid di-2-ethylhexyl ester, the C ₁₃ oxo acid diester of

Tetraethylene glycol, complex esters, synthetic oils of the type of polyglycols and the like.

The finished lubricating oils can also contain other additives, such as viscosity index improvers, z. B. polymethacrylic acid esters, polybutenes, oxidation retarders such as phenyl - «- naphthylamine, alkylphenols, Bisphenols, pour point depressants, dyes, wear-reducing agents such as zinc dialkyldothiophosphates, Sludge inhibitors.

45

Claims (1)

Claim: Mineral lubricating oil containing a reaction product of a phosphorus-sulphurized hydrocarbon, an alkylphenol or alkylphenol sulfide, calcium hydroxide or calcium oxide and carbon dioxide, characterized in that that it contains a reaction product, which in the presence of ammonium hydroxide or a mixture of ammonium hydroxide and ammonium sulfonate or an amine having 1 to 4 carbon atoms. 709 747/506 1.68 © Bundesdruckerei Berlin