DE2604342A1 - POLYURNANE LUBRICATING GREASES AND METHOD FOR MANUFACTURING THEM - Google Patents

Description

BP 28..

FEK 265 2>

BPH PAT 92

OLAWC -DELFS MOLL MCN3DCHL

PATENT LAWYERS

a HAMBURQ 13, POST BOX OBTTO

Deutsche BP Aktiengesellschaft 2 000 Hamburg 60, Überseering 2

Polyurea greases and methods of making them

The invention relates to a method for producing polyurea lubricating greases by joint implementation of a Monoamine »-, a diamino and a diisocyanato component in a lubricating oil as well as lubricating greases obtainable by these methods.

Lubricating greases of the type mentioned above with polyureas as thickeners are already known. So describes for Example U.S. Patent 3 2 ^ 3 372 Greases, the Polyureas of the general formula

R'-NH-f-CO-NHR " ¹ -NH-CO-NHR-N CO-NHR" ¹ -NH-CO-NHR ",

in which R ¹ and R "are monovalent and R and R" ^{1 are} divalent hydrocarbon radicals and χ is an integer from 1 to 3.

Greases according to the United States Patent No. 3,243,372 are prepared by mixing, dissolving the Dilsocyanat in d "lubricating oil which is to be concentrated, optionally with the aid of a further solvent, this mixture xu adds the amines, and then heating the Oesamtmischung, wherein the polyurea is formed in situ.

709833/0717

- 2 - 1/28/76 PAT 92

Are lubricating greases with polyureas as thickeners chemically resistant to water and oxidative influences; they decompose under the action of heat only at comparatively high temperatures.

DT-OS 2 260 ^ 96 describes a method of production improved polyurea greases through straight Implementation of a monoamino, a diamino and a diisocyanate » Component in a lubricating oil at elevated temperature, which is characterized in that one

as the monoamino component, a mixture of at least one representative of at least two of the classes of compounds of the general formulas

R-NH ₂ ,

R ^f -NH ₂ and

R "-OR" · -NH ₂ ,

where R and R "represent a monovalent aliphatic radical and R * represents a monovalent aromatic radical, R" ^{f represents} a divalent aliphatic radical,

a dioxa-alkane-diamine or a diamino component Mixture of dioxa-alkane-diamines of the general formula

NH ₂ -RO-R'-0-R "-NH ₂ ,

wherein R, R ¹ and R "represent divalent aliphatic ^ radicals,

709833/0757

- 3 - 1/28/76 PAT 92

and an aromatic diisocyanate as the diisocyanato component or a mixture of aromatic diisocyanates, with the two isocyanato groups in the molecules are linked to the same aromatic ring or to different aromatic rings,

used.

The lubricating greases of the OT-OS 2 260 ^ 96 are characterized by their chemical properties Resistance to water, oxidative influences and heat the end; they also have very good load-bearing capacity and excellent mechanical stability. In addition, wise they have an extremely low tendency to gel or harden.

However, the advancing technology places ever higher demands on the lubricants. So there was a need for lubricating greases that Withstand long periods of exposure to strong shear forces at normal and high temperatures. Of course you should such lubricating greases also have the beneficial properties of have known, polyurea thickened lubricating greases.

Surprisingly, it has now been found that greases are old excellent Mechanical-dynamic behavior, excellent flexing stability, very good load-carrying capacity and excellent thermal and chemical resistance is obtained if one uses a DT-OS 2 26O 496 a special diamino component containing oxygen bridges used.

The process according to the invention for the production of polyurea lubricating greases through joint implementation

a monoamino component consisting of a mixture from at least one representative each of the liaison

709833/07 5 7

classes of the general formula

R-NH ₂ and R * · - ₂ »

where R for a monovalent aliphatic and R * for is a monovalent aromatic radical,

a diamino component of the general formula

NH ₂ -ROR * -OR "-NH ₂ , in which R, R * and R" represent divalent aliphatic radicals,

and a diisocyanato component consisting of one aromatic diisocyanate or a mixture of aromatic diisocyanates, the two isocyanato groups in the Molecules are linked to the same aromatic ring or to different aromatic rings,

is characterized in that the diamino component is the

k, 17-Dioxaeicosandiamine-i, 20 of the formula

used.

The person skilled in the art could not expect the improved properties of the lubricating greases produced according to the invention in view of the prior art. According to DT-OS 2 260 k96 , of the dioxa-alkane-diamines mentioned there, the general »formula

709833/0767 * I

-5- 1/28/76 PAT ₉₂

NH ₂ -ROR ¹ -0-R "- ₂

Advantageously, those are used which ^{contain 2-4 carbon atoms in the radicals R and R "and 2-10 carbon atoms in the radical R 1} ; those dioxa-alkanediamines should preferably be those which contain 2-3 carbon atoms in the radicals R and R" and im Radical R * k - contain 6 carbon atoms.

The 4,17-DioxaeicosandLamin-i, 20 used in the present invention is technically relatively easily accessible; its manufacture is not claimed here.

The components are advantageously in the lubricating oil at a temperature of 21
implemented together.

a temperature of 20 to 15O C, preferably to 70 kO

If necessary, the mixture obtained is then further heated to a temperature of from 10 to 200 ° C., preferably to about 175 C, heated. Through this treatment under controlled Conditions an additional improvement in the properties of the lubricating greases of the invention is achieved, which presumably to transamidation and crosslinking reactions of the Polyureas is due.

According to a further advantageous embodiment of the invention, the diisocyanato component, optionally at a temperature above its melting point, or dissolved in lubricating oil or in a solvent inert under the reaction conditions, is added to the mixture of monoamino and diamino components and the lubricating oil . The diisocyanato component thus encounters an excess of amines during the entire reaction, which means that the degree of branching "or degree of crosslinking of the polyureas in the lubricating grease can be controlled in an advantageous manner"

709833/0757

• 3.

The molar ratio between monoamino component, diamino component and the diisocyanato component is preferably in the range from 2 t 1 I 2 to 2 t 1 2.5 or in the range from 2x2: 3 to 2 s 2 t 3.75 t with a stoichiometric Excess of diisocyanato component also crosslinking or branching of the polyurea chains occur, as a result of which the beneficial properties of the greases of the invention can still be improved.

The monoamino component contains the aliphatic monoamine or the mixture of aliphatic monoamines and the aromatic monoamine or the mixture of aromatic monoamines in proportion 6: 4 to 4: 6, preferably in a ratio of 1: 1.

For the production of the lubricating greases according to the invention, the monoamino component is advantageously used as the aliphatic monoamine a straight chain monoamine having 12 to 24 carbon atoms, preferably 16 to 24 carbon atoms, or Mixtures of such monoamines.

The aromatic monoamine used in the monoamino component preferably aniline, toluidine or xylidine or mixtures of these amines. Isomeric aromatic monoamines can be used individually or can be used as a mixture of xsomers.

The aromatic diisocyanato component used is advantageously Phenylene, tolylene, ditolylene, naphthylene or diphenylene methane diisocyanate or mixtures thereof. Isomers Diisocyanates can be used individually or as mixtures of isomers. ,

After cooling to about 100 ° C., the usual can suitably Lubricating grease additives are mixed in, for example to improve the boundary lubricating properties, the oxidation resistance, the corrosion protection or the like.

709833/0757 " ⁷ "

After cooling, the lubricating greases obtainable by the methods described above are prepared according to the methods described in FIG
Homogenized methods customary in practice.

Before homogenizing an additional amount of lubricating oil can be used
be added if you have initially set a higher concentration of thickener in the reaction mixture than is later desired in the finished lubricating grease.

Suitably the concentrations of thickener in the lubricating greases of the invention are in the range of 3 to 30 wt.

According to the present invention, any lubricating oil can be thickened. For example, paraffin-based or naphthenic-based mineral oil fractions of the lubricating oil boiling range or mixtures of such fractions, as well as synthetic lubricating oils such as polyaryl ethers, polyalkylene glycols, polysiloxanes and polyolefins, and also ester oils, are suitable
for example by reacting mono- and / or polybasic carboxylic acids with mono- and / or polyhydric alcohols.

The invention is illustrated by the following example
explained.

A very good grease of the same NLGI class (classification according to the National Lubricating Grease Institute) from the known prior art (DT-OS 2 200 k96, example i) is used for comparison. The listed values show that the lubricating grease according to the invention compared to the lubricating grease from the prior art with regard to flexing stability (change in penetration between 100,000 double strokes and 60 double strokes and change in the
Valkpenetration in the Shell-Roller-Test) and mechanical-dynamic

709833/0757

Behavior is far superior. Fall against these advantages the somewhat poorer value of the lubricating grease according to the invention for oil separation and the somewhat lower thickening capacity of the polyurea thickener used hardly weighs any.

example

A mixture of 75 · »6 g of k, 17-DioxaeicosandiaMin-i, 20, 25.6 g of p-toluidine and 73.5 g of GenamiiT 20/22 R 100 D (mixture of primary amines with chain lengths of C ₁ Q, C_ _o , C “ ₂ and C_r in the ratio 4 ι 39 ι 5Ί l 3) and 1,500 g of a naphthenic solvent raffinate (5 U / 50 C corresponding to 27.5 cSt / 50 ° C) is heated to 60 ° C with stirring. The amines melt and form a clear solution with the mineral oil. With constant vigorous stirring, 85 »3 g of Desnodur ⁰ ^ T (mixture of 65 96 2, ^ - and 35 % 2,6-toluene diisocyanate) are added dropwise within 15 minutes. The turbidity that sets in immediately increases rapidly and the entire contents of the reactor thickens. For rinsing, 100 g of the same base oil are added via the addition vessel for the diisocyanates. Then heating the reaction mixture with further stirring to 175 ° C, can, after reaching this temperature to 10O ⁰ C to cool, then is a mixture of 10 g Amine "'T (corrosion inhibitor of Ciba-Geigy), 20g Additiri ⁰ ^ 30 (Oxydationsinhibitor Bayer AG) and 110 g of base oil and then stirred until it cools, after which the lubricating grease is homogenized in a colloid mill.

- 9 709833/0757

- 9 - 1/28/76 PAT 92

Thickener content * dropping point (DIN 51 801, sheet i) i Valkpenetration (DIN 51 804, sheet 2) ι

Change in penetration between 60 DH and 100,000 DHl

Change in valke penetration in the shell roller test

a) after 48 h at 25 ° C

b) after 48 h at 90 ° C

Corrosion index according to Emcor test (DIN 51 802):

Oil separation according to IP 121/63 (1 Voche, 40 C) ι

Mechanical-dynamic SKF test Α run (2.5ΟΟ min, without heating)}

Individual results of the A run Wear of the cage rings Wear of the rollers » Residual fat: Oil coal:

Dry run t

-1

B run (1.5ΟΟ min " ¹ , 150 ^Q C) l

Individual results of the B run Wear of the cage rings Wear of the scooters Re s t fe t t t qty t Oil carbon:

Run dry 13 232

313 +47

+76 +90

Ge w. O "

3.3 Gev. #

passed brilliantly

9 mg 2 mg very good (93.6 wt. Tf) Grade 2 (low tarry residues)

none passed well

33 mg 23 mg good (88 wt. 56)

Grade 2 (low tarry residues)

none

- 10 -

709833/0757

Comparative example (DT-OS 2 26O 496. Example 1)

A mixture of 42.2 g of 4,9-dioxadodecan-i, 12-diamine, 63.6 g of Genamin ^ 20/22 R 100 D (mixture of primary amines with chain lengths of C ₁ Q, C ₃₀ , C ₂₂ and C ₂ ^ in the ratio 4: 39 x 54: 3), 22.2 g of p-toluidine and I.5OO a gemischtbasischen Solventraffinates (i4 ° e / 50 ° C g, corresponding to 105 cSt / 50 ⁰ C) with stirring at 60 ° C warmed up. At this temperature, the amines form a clear solution with the mineral oil. With constant vigorous stirring, 72.0 g of Desmodur ® T 65 (mixture of 65 % 2,4- and 35 % 2,6-toluene diisocyanate) are added dropwise over a period of about 10 minutes. The turbidity that sets in immediately increases rapidly and the entire contents of the reactor thickens. For rinsing, 100 g of the same base oil are added via the addition vessel for the diisocyanates. The reaction mixture is then heated to 175 ° C. with continued stirring, allowed to cool to 100 ° C. after this temperature has been reached, then a mixture of 10 g of Amine ^ T (corrosion inhibitor from Ciba-Geigy) and 20 g of Additin ^ jO (oxidation inhibitor from Bayer paint factories) is added ), 2 g Reomet ^ SBT (metal deactivator from Ciba-Geigy) and 168 g base oil and then stir until cool. After cooling, the grease is homogenized in a colloid mill.

Thickener content of the grease 1 drop point (DIN 5I 801, sheet i) i Walk penetration (DIN 51 804, sheet 2):

Change in penetration between 60 DH and 100,000 DHl -

Change in valke penetration in the shell roller test

a) after 48 h at 25 ° C +146

b) after 48 h at 90 ⁰ C +146

709833/0757

10 Weight 220 ⁰ C 287 + 163

- 11 -

1/28/76 PAT 92

Corrosion index according to. ' Emcor test (DIN 51 802):

Oil separation according to IP 121/63 (1 week, ^ O ° C) i

Mechanical-dynamic SKF test Α-run (2,5OO min, without heating) t

Individual results of the A run Wear of the cage rings Wear of the rollers: Residual amount of grease:
Oil coal:

Running dry

-1

B run (1,5OO min ', 15O C):

Individual results of the B run Wear of the cage rings Wear of the rollers: Re st fe t tmenget
Oil coal:

Running dry

1.3% by weight passed

75 mg k9 mg very good (93.3 wt. #) Grade 2 (low tarry residues)

none passed

16 mg 21 mg sufficient (71 wt. ^)

Grade 3 (strong asphalt-like residue)

none

- 12 -

709833 / 07Bf

Claims (9)

Claims 1. Process for the production of polyurea lubricating greases through joint implementation a Honoamino component, consisting of one Mixture of at least one representative each of the classes of compounds of the general formulas R-NH ₂ and R'-NH ₂ , where R is a monovalent aliphatic and R ^{1 is} a monovalent aromatic radical, a diamino component of the general formula NH ₂ -ROR ¹ -0-R "-NH ₂ , wherein R, R ¹ and R "represent divalent aliphatic radicals, and a diisocyanato component consisting of an aromatic diisocyanate or a mixture of aromatic diisocyanates, the two isocyanato groups in the molecules with the same aromatic ring or with different aromatic ones Rings are connected, characterized in that the diamino component is the k, 17-Dioxaeicosandiamine-i, 20 - 13 - 709833/0757 ORIGINAL INSPECTED -13- ».,. 7« PAX ₉₂ the formula used. 2. The method according to claim 1, characterized in that the components in the lubricating oil are reacted with one another at a temperature of from 20 to 150 ° C., preferably from kO to 70 ° C., and the mixture obtained, if appropriate, to a temperature of from 150 to 200 ° C., preferably heated to about 175 ° C. 3. The method according to claim 1 and 2, characterized in that that the diisocyanato component, optionally dissolved in Lubricating oil or a solvent which is inert under the reaction conditions, to the mixture of monoamino and diamino components and added to the lubricating oil. 4. The method according to claim 1 to 3, characterized in that that the aolar ratio between monoamino, diamino and diisocyanato component in the range from 2 t 1 J 2 to 2} 1x2.5 or in the range from 2: 2 t 3 to 2: 2: 3.75. 5. The method according to claim 1 to k, characterized in that the molar ratio of aliphatic monoamine or aliphatic monoamines of the general formula in the monoamino component R-NH ₂ to aromatic monoamine or aromatic monoamines of the general formula 709833/0757 -, * - 01/28/76 PAT ₉₂ 260A342 is in the range from 6 t k to k t 6 and is preferably 1: 1. 6. The method according to claim 1 to 5 »characterized in that that one in the monoamino component as aliphatic Monoamine of the general formula R-NH ₂ a straight-chain monoamine with 12 to 2k carbon atoms, preferably with 16 to Zk carbon atoms, or mixtures of such monoamines are used. 7 · Method according to claims 1 to 5 »characterized in that that one in the monoamino component as an aromatic monoamine of the general formula Aniline, toluidine or xylidine or mixtures of these amines are used. 8. The method according to claim 1 to 5, characterized in that that times as a diisocyanato component phenylene, tolylene, ditolylene, naphthylene or diphenylene methane diisocyanate or mixtures thereof are used. 9. Lubricating grease obtainable by a method of claims 1 to 8. 709833/0757