DE1063312B - lubricant - Google Patents

Description

GERMAN / ffiVm. PATENT OFFICE

kl. 23 c 1/01

INTERNAT. KL. C 10 IH

C 1OM 169 / OOA 28

EXPLAINING PUBLICATION 1063 312

N14912 IVc / 23 c

REGISTRATION DATE: APRIL 8, 1958

NOTICE
THE REGISTRATION
DND ISSUE OF
ATJS LEGAL:

AUGUST 13, 1959

It is known that metal-containing cleaning agents, such as organometallic carboxylic acid salts, naphthenates and / or sulfonates, quite effective in lubricating oils within a limited temperature range are. It is also known that certain non-ash-forming, oil-soluble, nitrogen-containing copolymers are also used from z. B. Lauryl methacrylate and polymerizable, nitrogen-containing compounds such as vinyl pyridines, N-vinyl lactams, acrylamides, and the like, lubricating oils have excellent cleaning properties within one give a wider temperature range than the metal-containing cleaning agents. Both the aforementioned, Metal-containing cleaning agents as well as the nitrogen-containing copolymers, however, are not favorable Properties at high pressures and heavy loads, and at very high temperatures, the polymers also unstable and cause the rings to stick, sludge formation and increase in viscosity of the lubricating oil.

Such oil-soluble nitrogen-containing copolymers, which in order to increase their oil solubility in addition to the polar nitrogen-containing substituents in the molecular chain also often have non-polar hydrocarbon radicals with more than 8 carbon atoms are also already in combination with known antioxidants such as organic phosphates and amines or Phenols, have been used, but the properties of the lubricating oils under high stress and not noticeably improved at high operating temperatures.

It has also been suggested to reduce engine wear through the use of such lubricating oils to fix which nitrogen-containing copolymers from, for example, acrylic acid esters with more than 8 carbon atoms in the alcohol part and vinyl pyridines and / or unsaturated esters of an amino alcohol together with halogen-containing phosphonic acid derivatives or basic sulfonic acid salts or neutral or basic metal salts contain carbocyclic carboxylic acids.

Certain organic phosphates, thiophosphates, sulphurized fatty materials, and chlorinated organics Compounds which are effective lubricants per se under high pressures and / or as stabilizers act in lubricating oil compositions containing metal-containing detergents, improve the However, the properties of the mixed polymer detergents do not, and such lubricating oil mixtures can therefore be used do not use when the engine is under heavy load.

It has now been found that such lubricating oils perform well under high pressures and are favorable Have stability properties, in addition to certain non-ash-forming, nitrogen-containing, as cleaning agents known copolymers also have a small amount of an aliphatic or aromatic I oil-soluble dithiocarbamate of a divalent metal lubricant

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Applicant:

N. V. De Bataafsche Petroleum Maatschappij, The Hague

Representative: Dr. K. Schwarzhans, patent attorney, Munich 19, Romanplatz 9

Claimed priority: V. St. v. America April 9, 195?

Julian Gilbert Ryan, Wood River, 111. (V. St. Α.), has been named as the inventor

from Group II of the Periodic Table.

The lubricants according to the invention thus exist

from a lubricating oil base and small amounts of a synergetic mixture of additives, namely a) an oil-soluble aliphatic or aromatic dithiocarbamate of a divalent metal of Group II of the Periodic Table of the Elements

and b) one or more copolymers with one Plurality of side chains COOR, where R is a hydrocarbon radical means having at least 8 carbon atoms. These copolymers are derived from (1) one or more esters of unsaturated carboxylic acids

with an aliphatic alcohol having at least 8 carbon atoms and / or a vinyl ester of a long-chain carboxylic acid and (2) an unsaturated nitrogen compound.
It is surprising to find such lubricants with

a content of nitrogen-containing polymeric cleaning agents, which do not behave favorably under stress show and are also not very stable, by the group of dithiocarbamates given above, which - as is known in the art - normally

act as antioxidants and corrosion inhibitors, the favorable properties when used under high load and a good stability are bestowed. The mechanism by which this combined The addition works is not yet clearly recognized, but

the synergetic effect achieved is clearly demonstrated by the test results given below.

The oil-soluble, nitrogen-containing copolymers preferably have a molecular weight of 50,000 to over 2 million, determined by the light scattering method.

The monomeric reaction components polymerizable with one another 1 and 2 can be used in a molar ratio of 1:10 Ms 10: 1 and preferably 1: 1 to 7: 1 will.

Suitable esters are e.g. B. esters of acrylic acid, a-acrylic-substituted acrylic acids with aliphatic alcohols of at least 8 carbon atoms and preferably 12 to 20 carbon atoms, such as decyl acrylate, Lauryl acrylate, stearyl acrylate, eicosanyl acrylate, docosanyl acrylate, decyl methacrylate, lauryl methacrylate, cetyl methacrylate and stearyl methacrylate.

The vinyl esters of long-chain carboxylic acids, such as vinyl aureate, vinyl palmitate, vinyl stearate, vinyl oleate, and long chain esters of vinylenedicarboxylic acids such as Methyl lauryl fumarate, are suitable polymerization components.

These components can be used alone or in admixture with one another. The technical lauryl methacrylate, which is derived from the commercial mixture of long-chain alcohols in the range from C ₁₀ to C ₁₈ , is obtained from coconut oil, is a particularly useful oleophilic component for the copolymerization.

The nitrogen-containing component of the polymers can consist of suitable monomeric compounds, containing primary, secondary or tertiary amino nitrogen, or from nitrogen-containing heterocyclic ones Links.

Examples are the amino-substituted olefins, such as p - (/? - diethyl-aminoethyl) -styrene; basic nitrogen-containing heterocyclic compounds which carry a polymerizable, ethylenically unsaturated substituent, e.g. B. the vinyl pyridines and the vinyl alkyl pyridines, such as 2-methyl-5-vinyl pyridine and 2- \ ⁷ ynyl pyridine.

N-vinyl lactams are also suitable. The vinyl radical is preferably unsubstituted (CH ₂ = CH -), but it can also be monosubstituted with an aliphatic hydrocarbon group of 1 to 2 carbon atoms, such as methyl or ethyl.

The vinyl pyrrolidones represent the preferred group of N-vinyl lactams. Examples are: N-vinylpyrrolidone, N- (1-methylvinyl) -pyrrolidone, N-vinyl-3,3-dimethylpyrrolidone and 5-cyclohexyl-N-vinylpyrrolidone.

Another group of nitrogen-containing monomeric compounds consists of the esters of amino alcohols and unsaturated carboxylic acids, for example / 3-methylaminoethyl acrylate, 4 - diethylaminocyclohexyl methacrylate and jS ^ -didodecylaminoethyl acrylate.

Amides of unsaturated carboxylic acids in which an amino substituent is carried by amide nitrogen, such as N- (yS-dimethylaminoethyl) acrylamide or polymerizable unsaturated amines, such as diallylamine, can also be used for the formation of the copolymers.

These polymers can also vary in amounts of about 5 to 30%, calculated on the end product, contain other polymerizable components, such as vinyl and aluminum formate or polymerizable unsaturated, short-chain hydrocarbons, e.g. B. ethylene, propylene, isobutylene, styrene, vinyl toluene and short-chain dienes such as 1,3-butadiene or isoprene; further unsaturated short-chain carboxylic acids and their derivatives, e.g. Acrylic acid, methyl methacrylate and butyl methacrylate; furthermore the short-chain, unsaturated ethers, especially the vinyl and aryl ethers.

The polymers can by a suitable method, such as. See U.S. Patent 2,737,452 are described.

The following examples explain copolymers which are used in lubricants according to the present invention are well usable, but the manufacturing process per se is not protected within the scope of the invention ίο claimed.

example 1

A mixture of about 4 moles of lauryl methacrylate, 1 mole of 2-methyl-5-vinylpyridine and 0.4 percent by weight of benzene peroxide was in a suitable reaction vessel for 2 hours at 80 to 85 ° C in a nitrogen atmosphere implemented. The substances that did not react were at 185 ° C and 1 mm pressure stripped. The copolymer obtained was a

zo rubbery product that is around 3 ° / ₀ nitrogen at a molecular weight of about 750,000 contained, and it was soluble in hydrocarbon oils.

Example 2

A mixture of 2.52 moles of stearyl methacrylate, 5.04 moles of lauryl methacrylate, 0.83 moles of methyl methacrylate and 1 mole of 2-methyl-5-vinylpyridine and 0.2 percent by weight of α, α'-azodiisobutyronitrile, dissolved in a small amount Acetone was left in a reaction vessel for about 24 to 48 hours at 65 ° C with stirring in a nitrogen atmosphere implemented. The polymer was then dispersed in an equal volume of benzene and with 5 to 10 parts by volume of a mixture of acetone and methanol are precipitated. This measure was repeated, and It was a stearyl methacrylate-lauryl methacrylate-methyl methacrylate ^ -Methyl-S-vinylpyridine polymer obtained with a nitrogen content of 0.60 percent by weight and a molecular weight of over 750,000.

Example 3

A mixture of about 6 moles of lauryl methacrylate, 1 mole of N-vinylpyrrolidone and 0.5 percent by weight of benzoyl peroxide was reacted in a suitable reaction vessel for about 10 hours at about 65 ° C. The polymer was dispersed in benzene and then precipitated with a mixture of acetone and methanol. This measure was repeated and a copolymer of lauryl methacrylate-N-vinylpyrrolidone with a nitrogen content of 0.45 percent by weight and a molecular weight over 250,000 isolated. The polymer contained the monomeric units in the same ratio as the starting mixture.

Example 4

A mixture of 1020 parts of technical lauryl methacrylate, 100 parts of methacrylanilide, 60 parts / I-diethylaminoethyl methacrylate, 300 parts of mineral oil and 3.6 parts of α, α'-azodiisobutyronitrile were at 60 ± 2 ° C stirred under nitrogen. Thickening of the batch was observed after 2 hours, and during the Over the next 16 hours, 900 more parts of the mineral oil gradually became as the polymerization proceeded admitted. In this way, an oil solution of a copolymer composed of the three polymerizable ones, which was just still stirrable, was obtained Compounds, essentially in the same molar ratio as the components fed, i.e. 86.4: 8.5: 5.1.

The technical lauryl methacrylate used above is the methacrylic acid ester of technical lauryl alcohol obtained by reducing the fatty acids in coconut oil. Such an alcohol mixture contains about 3% C ₁₀ -, 61% C ₁₂ -, 23% C ₁₄ -, 11% C ₁ - and 2% C ₁₈ -AlIcOhOIe.

Essentially following the procedure of the preceding Examples were also other polymers from mixtures of monomers in a molar ratio as indicated in Table I.

Table I.

example SMA *) LMA *) MMA *) MVP *) NVP *) S *) V 4.3 1 VI 4th 1 VII 2.25 4.5 1.86 1 VIII 1 1.2 IX 2.8 5.6 1 X 4th 1 2

*) SMA = stearyl methacrylate.
LMA = lauryl methacrylate.
MMA = methyl methacrylate.
MVP = 2-methyl-5-vinylpyridine.
NVP = N-vinyl pyrrolidone.
S = styrene.

The second essential additive in the lubricants of the invention is a dithiocarbamate and is preferred an alkyldithiocarbamate, which is particularly useful from a metal from group II B with an atomic number from 30 to 48, i.e. H. Zinc and cadmium.

Examples of such compounds are Ca, Ba, Zn or Cd - Dipropyldithiocarbamate, - Dihexyldithiocarbamate, - Di -2 - ethylhexyldithiocarbamate, - N - Amyl - N '- methyldithiocarbamate, -dicyclohexyldithiocarbamate, -diphenyldithiocarbamate and mixtures of these salts. The preferred Compounds are Zn and Cd diamyl or -Di ^ -äthylhexyldithiocarbamat.

The lubricating oils used in the lubricants according to the invention can be obtained from any paraffinic, naphthenic, asphaltic or mixed basic crude oil and / or mixtures thereof. The viscosity of these oils can vary over a wide range, for example, of 100 SUS at 37.8 ⁰ C to 100 SUS at 98.9 ° C. The hydrocarbon oils can be blended with fatty oils such as castor oil, lard oil, and / or with synthetic Lubricants, such as polymerized olefins, copolymers of alkylene glycols and alkylene oxides, silicone polymers, for example dimethyl silicone polymers.

Particularly desirable mineral lubricating oils are crude oils from West Texas, Ellenburger, East Texas, Oklahoma and California. A well-suited solvent refined East Texas mineral lubricating oil had the following Characteristics:

Pour point - 12.2 ° C

Viscosity 27 cSt at 37.8 ⁰ C

Viscosity index 95

The two synergistic types of additives are present in the lubricating oil blends in abundance from about 0.1 to 10 percent by weight each and preferably from about 0.5 to 6 percent by weight, calculated on the finished lubricating oil mixture.

Preferred mixtures according to the invention are illustrated by the following list:

Mixture A

Copolymer according to Example 3 5.5 percent by weight

Zn diamyldithiocarbamate 0.4 percent by weight

Mineral oil remainder

Mixture B

Terpolymer according to Example 2 5.5 percent by weight

Zn diamyldithiocarbamate 0.4 percent by weight

Mineral oil remainder

Mixture C

Copolymer according to Example 3 5.5 percent by weight

Cd diamyl dithiocarbamate 0.5 weight percent

Mineral oil remainder

Mixture D

Copolymer according to Example 3 5.5 percent by weight

Zn diamyldithiocarbamate 0.5 percent by weight

Zn-dimethylcyclohexylthio-

phosphate 0.92 percent by weight

Ca basic petroleum sulfonate 1.0 percent by weight

Sulfated ash

Bright stock 6 percent by weight

Mineral oil remainder

Mixture E.

Terpolymer according to Example 7

Zn diamyl dithiocarbamate

Zn-dimethylcyclohexylthio-

phosphate

Basic Ca petroleum sulfonate

Mineral lubricating oil

Mixture F

Copolymer according to Example 1

Zn diamyl dithiocarbamate

Zn-dimethylcyclohexylthio-

phosphate

Basic petroleum sulfonate

Mineral lubricating oil

5.5 percent by weight 0.5 percent by weight

0.92 percent by weight 1.0 percent by weight

Sulfated ash
rest

5.5 percent by weight 0.4 percent by weight

0.92 percent by weight 1.0 percent by weight

Sulfated ash
rest

The extraordinary properties of such lubricants according to the invention are summarized in Table II, on the basis of a test in the Timken machine with regard to the load properties and in the Cadillac engine under the heaviest load in driving tests on country roads and in the COT engine an 80-hour test for cleanliness, corrosion and overall engine behavior at high temperatures.

The Timken test is described in the SAE Journal, 28,

Pp. 53 to 60 (19.31). The test conditions in the Cadillac engine and the COT engine were as follows:

A. Cadillac engine 3150 to 3250 rev / min.

oil temperature 93.3 to 104.4 ⁰ C

Jacket temperature 65.6 ° C

Carburetor air temperature ... 32.2 to 43.3 ° C

Idle ί minute

Time 100 hours

B. COT engine (CRC single cylinder engine 2800 rev / min.

Jacket temperature 190.6 ⁰ C

Oil temperature 135 ⁰ C

Carburetor air temperature ... 43.3 ⁰ C

Time 80 hours

Table II

mixture Tiniken
load
in kg Cadillac test *)
I.
Mud! total
education ■■ deposit deposit
at the inlet
Valve COT motor test
Weight
loss
of the camp
in mg D (according to the invention)
E (according to the invention)
Mixture X **)
A (according to the invention)
Mineral lubricating oil
Mixture Y ***) 12.70
12.70
7.26
13.61
4.54 90 ^; 91
95 ι 90
60: 78
I.
I.
SO! 50
50! 85
80
68
60
70 267
1157

*) 100 = very good. 0 = bad.

♦ *) Mixture X is the same as mixture D, but without zinc diamyldithiocarbamate. ** ♦) Mixture Y consists of mineral lubricating oil with an addition of 0.5 weight percent Zn diamyldithiocarbamate.

When testing mixtures B, C, E and F in the Timken machine and in the Cadillac engine results were similar to those of mixture D. Mixtures B, C, D, E and F prevented the examination in the COT Mascliine the corrosion, and the engine was clean and in good condition. On the other hand, if the Zn dialkyldithic carbamate was omitted from these mixtures and these in the manner described above with respect to their Behavior under high stress were tested, the results were poor (about the same as for Mixture X), and the machines were in poor condition at the end of these tests.

A test was also carried out with a Lauson engine under the following operating conditions :

Speed 2150 rev / min.

Load 90 ° / ₀ fully throttled

(about 3,042 hp)

Jacket temperature 218.3-4.1 ° C

oil temperature 107.2 + 1.1 ° C

Air-fuel ratio 13: 1

Ignition setting 15 ° BTC

Oil change 1.134 kg

The following results show the synergetic effect of the mixture of additives according to the invention in Comparison to the effect of the individual additives.

composition

Lacquer formation in deposits

Piston ring bonding

(1) mineral oil

(2) Mineral oil + 3 ° / ₀ mixed polymer of lauryl methacrylate and N-vinylpyrrolidone

(3) Mineral oil + 0.5% Zn diamyldithiocarbamate

(4) Mineral oil + 2 ° / ₀ mixed polymer + 0.5 ° / ₀ Zn-diamyldithiocarbamate

Evaluation: 10 = very good. I) - bad.

The new lubricating oils can also contain small amounts (0.1 to 3%) of other known agents as additives contain, such as metal dithiophosphates (Zn-alkyldithiophosphate), organometallic sulphonates, e.g. neutral or basic Ca, Ba or Zn petroleum sulphonate, amines, such as Phenyl-ct-naphthylamine, alkylphenol, improvers for the Viscosity index and pour point depressants, such as the alkyl methacrylate polymers and especially those which are described in U.S. Patent 2,710,842. Furthermore, condensation products from chlorinated Paraffin and naphthalene; Extreme pressure additives, such as amine salts of trichloromethane-phosphinic acid, their esters, Amides or amine salts; organic sulphides and mixtures of such substances.

The lubricants according to the invention are used as machine oils, turbine oils, gear oils and , in various other areas of lubrication, in which keeping clean and preventing wear are essential.

3.5

9.5

10

Claims (7)

Patent claims: 1. Lubricant consisting of a lubricating oil and a smaller amount of a synergistic one Additional mixture of a) 0.1 to 10 percent by weight, based on the total mixture, of one as Lubricant additive, known per se, oil-soluble aliphatic or aromatic dithiocarbamate of a divalent metal from Group II of the Periodic Table and b) 0.1 to 10 percent by weight, based on the total mixture, one or more known per se as a lubricant additive oil-soluble copolymers with a plurality of side chains COOR, where R is a hydrocarbon radical with at least 8 carbon atoms means from (1) one or more esters one unsaturated carboxylic acid with an aliphatic alcohol having at least 8 carbon atoms and / or a vinyl ester of a long chain carboxylic acid and (2) an unsaturated nitrogen compound. 2. Lubricant according to claim 1, characterized in that the unsaturated nitrogen compound the copolymer has a heterocyclic ring system and a vinyl pyridine or a vinyl lactam, in particular is an N-vinyl pyrrolidone. 3. Lubricant according to claim 1, characterized in that the unsaturated nitrogen compound of the copolymer is an ester of an amino alcohol and an unsaturated carboxylic acid, such as Diethylaminoethyl methacrylate. 4. Lubricant according to claim 1 to 3, characterized in that the oil-soluble copolymer has a molecular weight of 50,000 to 2,000,000. 5. lubricant according to claim 1 to 4, characterized characterized in that the monomeric components (1) and (2) in the copolymer in a molar ratio from 10: 1 to 1:10 are available. 6. Lubricant according to claim 1 to 5, characterized in that the oil-soluble dithiocarbamate is derived from zinc, cadmium, barium or calcium. 7. Lubricant according to claim 1 to 6, characterized by a further content known per se Lubricating oil additives such as a viscosity index improver, a pour point depressant or one High pressure additive. Considered publications: German Patent No. 947 186; German interpretation document N 8941IV c / 23 c (published at 13th. 9.1956); French patents nos. 1 061 771, 1101 147, 111 338, 1 131 152. Legacy Patents Considered:
German patents No. 1 003 896, 1 003 897. © 909 607/367 8.59