DE1769115C - lubricant - Google Patents

Description

I 769 1 15

The Lrligation lieirilli lubricant, consisting of a larger proportion of oil with a lubricating viscosity and Eiiieiii smaller area in the range of 0.01 to 10 percent by weight based on the weight of the entire lining / .thirting - one Derivative of dihydrocarbyldithiophosphoric acids as an additive, optionally together with conventional ones Additives.

It is known that the metal salts of the diesters of phosphorothiolthioiic acids, which are generally known as Dithiophosphoric acids are useful additives for lubricants. The Diester can be prepared by reacting alcohols or phenols with phosphorus pentasullide and then converted into the metal salts by direct reaction with a metal oxide or hydroxide.

Olmohl salts of a wide range of metals al ·. Additives for lubricants with a larger one If a lower degree of efficiency has been proposed, the zinc salt is grounded because of its greater solubility and the ease of their production almost • !!

It has been known for some time that organic zinc dithiophosphorus, when used as additives for lubricants, are effective inhibitors of oxidation and corrosion of metal build-up, such as. I !. Copper P.lei, are bearings and enlarge the llclaslharkciltkapazilät of the oil. These compounds have / u reduce the valuable leagues shaft, the wear of valve lifters, de ^r occurs gelegentiich under high liclustuiig.

As already mentioned, the present study concerns a lubricant that consists of a

larger proportion of an oil of a selining viscosity, viscosity and a smaller proportion of an additive, comprising the mixture of an oiler of several Bismutilihydroearbyldithiophosphate with one oiler several zinc oilers cadmkiin dihydrocarbyldithiophosphates.

The hydrochloride group can be alkyl, alkaryl, aralkyl or aryl, where the group can be substituted by hydroxyl, halogen or ether groups. The hydrocarbyl groups of some acidic Components of the mixture can be the same or different, and mixtures of acids can be in the production of additives be used.

The amount of bismuth in relation to the total weight of bismuth and / ink and / or (', ulinium in the dihydrocarbyl ditliophosphates is usually 5 "/ ,,. Preferably IO to') 0" /, i and especially IO to 6 () ",". In a preferred embodiment of the invention, bismuth is present in an amount of 10 to M) percent by weight of the total weight in the dihydrocarbons, bismuth and / or cadmium present in phosphates.

In another preferred Au-.iuliniiigform the Irliiulimg the additive of the sterile agent is an essentially neutral mixed salt, with one or more DiliydiocarhyMilhiopliosphorsüiren. revealing both bismuth and either / ink or cadmium, which for example duii.li partially «neutralizing the 1) illiiophospliorsaiirenikr mixtures of acids with Wi.sntuloxyd or with a mixture of bismuth and / ink or cadmium * oKydcfi can be produced, whereby the Lmliicutralisatiousstiife can be carried out by further IJinset / s with / ink or Ciidmiumüxyd. In this way, essentially neutral products can be obtained, whereas it is generally not possible to obtain bismuth lithium phosphate free from acidic impurities when bisnuit oxide is used.

The lubricating oil additives are made by partially neutralizing a dihydrocarbyl dihiophosphoric acid or a mixture of dihydro-

iQ carbyldithiophosphoric acids with Wisinutoxyd or hydroxide or with a mixture of bismuth oxide or hydroxide and zinc oxide or hydroxide or Cadmium oxide or hydroxide. The egg II serve product wirii ι ,, it zinc oxide or hydroxide> .er cadmium oxide or hydroxide implemented, with one essentially neutral mixture of one or more bismuth dihydrocarbyl dithiophosphates and one or more zinc or cadmium dihydrocarhyldithiophosphates is obtained.

* ° By "essentially neutral" is meant, that either

1) the acidity of the salt when determined in a solution consisting of 60 percent by volume

₂ . Benzene and 40 percent by volume of neutralized

industrial denatured alcohol containing ImI lacmoid indicator per KX) ml of solvent, is not more than about 1 mg KOH / g, or

2) the solution is preferably neutral or alkaline to the indicator or that

3) the pH of the salts is greater than 4 and preferably greater than 5 when in a pH meter by dissolving 1.5 g of a sample in a mixture of 60 ml of aqueous alcohol (67 percent by volume Alcohol, 33 percent by volume of water) and 40 ml of ether.

The additives in the context of the present invention show when compared with the corresponding usual Zinc dialkyldithiophosphates improved resilience properties on. They also give the oil improved resistance to oxidation. In comparison with the corresponding simple bismuth dithiophosphates the essentially neutral ones have mixed Salts prepared as described above provide improved thermal stability in lubricant preparations and show less tendency to cause wear under low load.

The Diliydrocarbyl (Jithiophospho ^r <äure or hybrids thereof can be prepared by reaction of einehi or more alcohols or phenols, or a mixture thereof may be prepared by Phosphorpuitasulfid.

The mixtures of the salts can be separated by

.Vi Manufacture of one or more Wisinut-dihydroearhvldithiophosphate and one or more dihydrocarbylditliiophospliatc of / ink or cadmium and subsequent / iisainnieninischeii der S, il / e will. The alcohols, which alone are oiler in mixture

fio for the Hüraltillimi! of dihydroearbyldithiophosphoric acids can be selected from the range of the following alcohols:

Isopropyl alcohol
ii-llulylalkoliol
hobutyl alcohol
ii-l'enlyl alcohol
1,3-dimethylbutyl alcohol

I 769 I 15

Mixed straight alcohols with 6 to 10 Carbon atoms

Cupryl alcohol (I-Mcthylhcptylu
2-ethylhexyl alcohol
n-octyl alcohol
2,2,4-trimethylpentyl alcohol

n-decyl alcohol
isodeeyl alcohol
isolridecyl alcohol

The IMiCiH) Ie küiiiiLii alkylierie phenols, in particular p-OelylpheiKil, p-Nonylphenol and Heptylphenol The mixtures of salts within the scope of the present Invention may be from any of the acids or mixtures of acids such as those used in the British Patent 822,655 are described, be formed.

Any hydroearbyl group in the dihydrocarbyl dithiophosphate can vent 3 to 8 carbon atoms.

The proportion of the additive in the lubricant is 0.01 to 10 percent by weight, preferably 0.1 to 2.0 percent by weight - based on the weight of the preparation.

The lubricants according to the invention can also contain the usual additives, such as Z. Π. Viscosity index improver. Corrosion inhibitors, cleaning agents, dispersants, etc. The preparations are preferably alkaline metal sulfonate cleaning agents or Harium salts from phosphorsulfuriert.'i hydrocarbons, such as polyisobutylene, ash-free dispersants such as ζ. Β Polyisobutenyl-Succinhniden and viscosity index improvers, such as L. B. liingket'igen alkyl polymethacrylals or polyisobutylene.

The production of the additives in the context of the present study will now be carried out with reference to the the following work instructions.

1. Manufacture of
Bismuth-zinc (1: I) salt from DTPA-I

The phosphorodithioic acid (DTPA-I) was added to, laughs, by the gradual addition of Phovphorpentasullid 4BOg, 2, KiMoI) / u a mixture of isohuianol, (510 g, 6, ¹ ) mol) and mixed l'entanols (2Mj-I 3, 0MoI) at a level sufficient to allow access at a temperature of around 65 ° C. Stirring was continued until the development of H.jS F. had essentially ended.

It was now a slurry of bismuth oxide (i3, ') 7 μ, 0.03 mol) and zinc oxide (Vg) in one Mineral oil (24 g) in one with stirrer. Cooler and

ίο drip funnel provided piston manufactured.

The phosphorodithioic acid (133 g, 0.5 mole) was slowly added to the dropping funnel Drop rate added while maintaining temperature at about 60 "C (about 30 minutes).

The remainder of the zinc oxide was then added, making the total amount of zinc oxide added 14.52 g (0.178 mol) and the mixture was then stirred at 60 ° C. for an additional hour. The product was then in a vacuum at uwa KO C for Removal of the excess of alcohols with a 10 mm pressure stripped off.

The additive thus obtained was compared to a laemioden Indicator was alkaline and had a pH of (), 5. It had the following analysis:

Bi ...

Za ...
P.

(Calculated 6.56 "/.)
(Calculated 6.35 ¹ V _n )
(Calculated ".%"/")

The weight ratio of bismuth and zinc in this mixed salt, was therefore approximately 1: 1.

Further production examples for the production

of the connections within the scope of the present disclosure are listed in Table I, the same dithiophosphoric acid used as in step 1 and the manufacturing process was essentially the same in all cases. One and only The difference was in the ratio of Wismutox> d

1 »/ u of zinc oxide applied. All these products' were alkaline to a lacmoid indicator and had pH values ranging from 6.1 to 6.6.

Table I Bismuth zinc dithiophosphate from DTPA

Implementation example
No. ZnO
Weight B. (I. l »l 18.2 0. 224 2 20.0 0. 246 3 21.45 264 4th

"/" Tue Loading Ge Ge icchnct found unJcr 3.85 8.45 3.41 2.18 8.63 1.77 0.94 ¹ J.49 0.91

Zn

lie

calculate!

7.72
8.63
9.3K

Gessiclil--

verbiilini-.

lii: / m

2
4th
10

5. Manufacture of
Bismuth- / mk- (l: I) -SaIz v..n DIPA-:

A mixture of dialkyldilhiophosphoric acids was made from Isopropaiiol (IWg, .1,3.1 Mol), Caprylalkollol (600 g, 4.62 mol) and PhosphorpentasuHid (.17K g, 1.7 mol) in Afbeitsvorschnft 1 described Way, but made at a temperature of 80 Γ.

Using a procedure borrowed from the toilet as described in Section I, the dithiophosphorus compound (DTPA-2) (16 ') g, 0.5 mol) was added to a mineral oil slurry of wisimil and zinc oxides, and the reaction was carried out by adding white zinc oxide completed as described in working instruction I. The weights of ai L'ewaiullem bismuth and / inkoxul were 13. ^{1 |} 7μ (0.03 Mc ¹ U or 14.52 g (0.17k'Mo1). The product had a width of 0.7 mjz KOII g and a pll of 5.3.

Sn An analysis showed the following values:

Di ... (., 4% Zn ... 4, ') "/" P 7.44 ¹ V ₁₁

(Calculates 6.2 "")
(Calculated <>. 4 "/")
(Calculated 7.8 "',,)

6. Manufacture of Wisinut-Zink- (1: I) -SaI /. of di- (2-ethy1hexyl) -dithiophosphoric acid

Using essentially the same Procedure as described in working instruction I.

Di-i-Atliyl hexykliihionhosphorsiiire (111 g, 0.2 mol), prepared from 2-Äthyllr.xanol (1,040 g, ₁ H O mole) and Pliosplmrpiinlasullid (444 g, 2.0 mol) hei KO to 90 "C , / u of a milking oil slurry of bismuth oxide and zinc oxide were added, the weights of bismuth and zinc oxides used being K.4 μ (0.018 mol) and 75 g (0.107 mol). The product had an acidity of 0.93 mg KOH / g and a pH of 4.7. Its analysis was as follows:

Bi ... 4.3% (calculated 5.15%)> °

Zn ... 4, h% (calculated 4.95%)

P 6.75% (calculated 6.45%)

7. Production of bismuth-cadmium (1: I) salt
of di- (2-ethylhexyl) -dithiophosphoric acid, ₅

Using essentially the same procedure as described in Preparation 1 Di-2-ethylhexyldithiophosphoric acid (114.3 g, 0.3 mol), from a subsequent preparation similar to that in Example 6 for a mineral oil slurry »On bismuth oxide and cadmium oxide added, with the weights of bismuth and cadmium oxides 11.6 g (0.025 mol) and 11.3 g (0.09 mol) ^ respectively.

The product had an acidity of 0.56 mg KOH / g and a pH of 4.4. His analysis was as follows:

Bi

CD

P ..

ς / "η / / η , .1,. /. ü η / »

- ', * - »/ 0 V ₄ UUl LHlIlCl Ii ₁ Il Iq)

7.3% (calculated 6.6%)

6.46% (Calculated 6.1%)

30th

8. Preparation of bismuth salt of DTPA-I
This was prepared as described in Preparation 1, with the exception that all of the bismuth oxide (42.7 g, 0.0917 mol) was added at the beginning of / u of the DTPA-I (133 g, 0.5 mol). Twice the normal amount of mineral oil (48 g) was required to obtain a clear solution. The additive had the following analysis:

Bi ... 15.0% (calculated 14.7%)

P 6.59% (calculated 6.64%)

The additive was obtained by mixing 20 percent by weight of the bismuth salt prepared above with 80 percent by weight of a similarly prepared zinc salt of the same acid.

Antioxydicrcnden the properties of the additives to demonstrate the present invention in a typical lubricating oil compositions were prepared in a mineral oil A, which was a refined Mincralöllösiingsmitlel a viscosity of about 160 Redwood seconds at 60 1 C ^c. These minerals were all adjusted to a phosphorus content of 0.072%, and comparative tests were carried out with certain common zinc dialkyl dithiophosphates and with bismuth dialkyl dithiophosphates which did not contain any zinc or cadmium. These oils were subjected to the known rotary bomb test, is given by the description in British Patent 1,023,380 on page 12, lines 5 to 22nd The results of these tests and the conditions used are set out in Table II. The advantage of the additives contained in the lubricant according to the invention over the corresponding zinc or cadmium dithiophosphates can be clearly seen from this table, and in some cases the additives within the scope of the present invention even show an advantage over the simple bismuth pulps.

Home comparison of the resilience properties of the lubricants containing the additives mentioned with lubricants containing the corresponding zinc dithiophosphates on the 4-ball machine at room temperature according to the standard method, which involves a series of! • ■ minute runs at different Applying loads, a marked improvement in the load-bearing capacity is consequently obtained, as can be seen by comparing the wear and tear diameter at loads above the point of the beginning of seizure. In general, it has been found that the higher the amount of bismuth dithiophosphate in the oil, the smaller the wear scar diameter. However, when wear tests have been carried out on the 4-ball machine at low loads, the degree of wear as obtained by bismul dithiophosphate is considerably greater than that obtained by the corresponding zinc dithiophosphate. The lubricants according to the invention with the additives mentioned, in particular the essentially neutral products such as Sij. obtained by the preferred manufacturing process, often show a smaller increase in wear than as could be inferred from the amount of bismuth present. This is illustrated in Table UI which compares the test results with mixtures of several dithiophosphates in Mineral Oil A, all of these mixtures containing 0.056% phosphorus. The 4-ball machine was operated währenJ periods of one hour period under a 15 kg load at an oil temperature of 50 ⁰ C. It can be seen from Table III that the additives contained in the lubricant according to the invention gave wear scar diameters under these conditions which did not exceed those of the corresponding zinc dithiophosphates too much, whereas the simple bismuth salts showed an essentially increased wear.

Table!!
Rotary bomb test

Temperature 150 ⁰ C

3 meters of copper wire

Initial pressure 6.33 kg / cm "

Additives 7th Induction
neiiotie
Minutes None 0.75
1.08
0.8!
0.80
0.78
0.77
0.98
0.975
0.97
1.22
1.17
LlI 26th
? 33
275
309
281
280
249
196
240
237
280
271
306 Zinc salt of DTPA-I
Bismuth salt from DTPA-I ....
Product from manufacturing
example 1
Product from manufacturing
example 2
Product from manufacturing
example 3
Product from manufacturing
example 4
Zinc salt of DTPA-2
Bismuth salt of DTPA-2
Product from example 5
Cadmium-di- (2-ethyhexyl) -
dithiophosphate
Bismuth di (2-ethylhexyl) -
dithiophosphate
Product from BeisDicl 7

Table III

4-ball wear test (15 kg -! Hour - 50 ⁰ C)

Additives

Middle β / Wear scars Io diameter mrn 0.58 0.296 0.84 0.433 0.625 0.325 0.62 0.286 0.61 0.313 0.60 0.300 0.87 0.296 0.915 0.400 0.83 0.312

7th

Increase in wear and tear

opposite to Zn compound

Zinc salt of DTPA-I

Bismuth salt from DTPA-I

Product from preparation example 1

Product from preparation example 2

Product from preparation example 3

Product from preparation example 4

Zinc di (2-ethylhexyl) dithiophosphate
Bismuth di (2-ethylhexyl) dithiophosphate
Product from preparation example 6

Claims (5)

Patent claims: 1. Lubricant, consisting of a larger proportion of oil with lubricating viscosity and a smaller proportion in the order of magnitude of 0.01 as to 10 percent by weight - based on the weight of the total lubricant - a derivative of dihydrocarbyldithiophosphoric acids as Additive, if necessary together with conventional additives, characterized in that that the lubricant as derivatives of dihydrocarbyldithiophosphoric acids a mixture of one or more bismuth dihydrocarbyl dithiophosphates and one or more zinc powders Contains cadmium dihydrocarbyl dithiophosphates. 2. Lubricant according to claim 1, characterized in that it is a mixture of dihydrocarbyl dithiophosphates contains whose hydrocarbyl groups are alkyl, alkaryl, aralkyl or aryl groups may be, optionally by hydroxyl or ether groups or by one or several halogen atoms can be substituted and 3 to 3 15, preferably from 3 to 8 carbon atoms. ♦ ' 3. Lubricant according to claim 1 or 2, da- 46 10 zero
6th
1 35
5 characterized in that it contains a mixture of dihydrocarbyldithiophosphates in which the amount of bismuth present 5 to 90 Ge weight percent, preferably 10 to 60 weight percent - based on the total amount of weight of bismuth and zinc and / or cad present mium amount - in the dihydrocarbyldithiophosphates. 4. Lubricant according to one of claims 1 to 3, characterized in that there is a substantially neutral mixture of bismuth and zinc or cadmium dihydrocarbyldithiophosphates contains. 5. Lubricant according to one of claims 1 to 4 “characterized in that it is a mixture of bismuth and zinc or cadmium dihydrocarbyldithiophosphates, which are partly due to: Neutralizing a dihydrocarbyldithiophosphoric acid or a mixture of dihydrocarbyldithiophosphoric acids with bismuth oxide or hydroxide or a mixture of bismuth oxide or bismuth oxide hydroxide and zinc oxide or hydroxide or cadmium oxide or hydroxide and further conversion of the product with zinc oxide or hydroxyc or cadmium oxide or hydroxide is.