DE1075775B - Lubricating oil mixtures - Google Patents

Description

GERMAN

The invention relates to lubricating oils which are particularly suitable for lubricating under very high conditions severe conditions, e.g. B. under very high pressures, at high speed and high temperature.

It is known that the high pressures that occur in certain types of gears and bearings are a Can cause the lubricating film to tear, resulting in damage to the machine can. It has been proven that lubricating oils, such as mineral or synthetic lubricating oils, their protective effect on rubbing surfaces can be improved by adding certain substances, so that excessive wear and tear, scoring and galling, which normally result in a cracking of the lubricating film follows, can be prevented even under very unfavorable pressure and speed conditions can. Lubricants that have this very desirable property are commonly referred to as extreme pressure lubricants designated.

It is known that compounds containing certain elements such as chlorine, sulfur, phosphorus and lead can impart extreme pressure properties to lubricants, and such compounds become Called high pressure additives. The chlorine-containing compounds used include diesters of chlorine and acid and chlorinated terpenes.

However, such diesters do not give the lubricating oils sufficient extreme pressure properties for many purposes, especially if the lubrication points concerned are exposed to higher temperatures.

Reaction products of hexachlorocyclopentadiene and reactive thio compounds have also become known, in which the two chlorine atoms in 5 positions are replaced by RS— radicals. These Compounds are also said to have a certain effect as extreme pressure additives. You let yourself further implement with unsaturated carboxylic acid anhydrides or esters to endo compounds that can be converted into acids by hydrolysis. These acids are said to have rust-preventing properties exhibit.

It has been found that lubricating mixtures containing a minor proportion of hexachlorocyclopentadiene or a reaction product of a cyclopentadienyl compound with the general formula _v

Lubricating oil mixtures

Applicant:
"Shell" Research Limited, London

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

Claimed priority:
Great Britain March 13 and December 10, 1957

Vernon Warner David, Chester, Cheshire,

and Francis Henry Waight,

Eastham, Wirral, Cheshire (UK),

have been named as inventors

an ethylenic or acetylenic bond, but no carboxylic acid, anhydride or ester groups and which has at least 1 chlorine or bromine atom if all X represent hydrogen atoms, contain favorable high pressure properties. In the above formula, X can be hydrogen, chlorine, or Bromine atom mean.

The reaction products used in the compositions of the invention are usually, but not necessarily, Diels-Alder adducts. The Diels-Alder reaction applied to the present Cyclopentadienyl compounds corresponds to the two general ones given below Reaction schemes:

X-C

X-C

• X

C-X

50

c I c

cx _a -1- Ii!

.R ₁

R ₂

X-C *

'Cx ₂

and an unsaturated compound containing at least or

90S 730/445

x-c

X-C.

cC x-c

CX ₂ +

X X

X-C,

CX,

In the formulas, each X represents a hydrogen, chlorine or bromine atom. R ₃ and R ₄ each represent a hydrogen, bromine or chlorine atom or a hydrocarbon radical. R ₁ and R _{2 represent} a hydrogen, chlorine or bromine atom or an organic radical, or they together form part of a carbocyclic, polycarbocyclic, heterocyclic or polyheterocyclic ring system, the radicals R ₁ and R ₂ not being carboxylic acid, anhydride or ester groups or included. When all Xs in the cyclopentadienyl compound are hydrogen atoms, the unsaturated compound should contain at least one chlorine or bromine atom.

The reaction products used as additives can also be an epoxy, episulfide, episulfone, Contain episulfoxyd or an ethyleneimine group.

In the above formulas, R ₃ and R _{4 are} preferably a hydrogen or chlorine atom. If R ₃ and R _{4 represent} hydrocarbon radicals, those radicals with not more than 3 carbon atoms are preferred.

If the radicals R ₁ and R _{2 are} separate radicals in the above formulas, preference is given to those compounds which contain alkyl groups, chlorinated alkyl groups or oxyalkyl groups. An example of a compound of type II in which both R ₁ and R _{2 represent} oxyalkyl radicals is dichloro-7,7-endomethylene-1,2,3,4-tetrachloro-5,6-dioxymethylcyclohexene. This compound can be prepared by reacting hexachlorocyclopentadiene with 1,4-dioxybutene-2,3. Examples of other dienophilic components which can be reacted with hexachlorocyclopentadiene to produce compounds of this type are vinyl chloride, ethylene, propylene, dichloroethylene and tetrachlorethylene.

Particularly preferred high-pressure additives according to the invention are compounds of type I and II in which R ₁ and R ₂ together represent part of a carbocyclic, polycarbocyclic, heterocyclic or polyheterocyclic ring system. The radicals R ₁ and R ₂ , together with the carbon atoms 5 and 6, can form a cyclopentane or cyclopentene ring which can contain halogen atoms bonded to the carbon atoms. Examples of such compounds are those which can be produced by a Diels-Alder reaction between hexachlorocyclopentadiene and cyclopentene or cyclopentadiene or tetrachlorocyclopentadiene. According to another embodiment, the radicals R ₁ and R ₂ together with carbon atoms 5 and 6 can form a cyclohexane or cyclohexene ring, such as. B. in the Diels-Alder adducts of hexachlorocyclopentadiene and cyclohexene or cyclohexadiene.

Very particularly preferred extreme pressure additives according to the invention are those in which R ₁ and R ₂ together with carbon atoms 5 and 6

form part of a di- or tricarbocyclic ring system, e.g. B. an endomethylene cyclohexene ring. Such compounds can also be modified by introducing an oxygen or Sulfur atom or an amino group instead of an ethylenically unsaturated carbon-carbon bond. These compounds not only contribute to the achievement of very good high pressure properties, but also have reduced volatility and are therefore more suitable for use in lubricating oils than the compounds with lower molecular weight. Among these compounds are the following specified particularly preferred:

1,2,3,4,10,10-HeXaChIOr-1,4,4a, 5,8,8a-hexahydroendo-1,4-exo-5,8-dimethylene naphthalene or a preparation containing 90% by weight of this compound which is the Diels-Alder adduct of hexachlorocyclopentadiene and bicyclo- (2.2.1) -2,5-heptadiene, the preparation of which is described in British Patent 692,546 is described.

1,2,3,4,10,10-hexachlor-o ^ -epoxy-1,4,4 ^ 5,6,7,8, 8 a-octahydro-endo -1,4-exo-5,8-dimethylene naphthalene or a preparation containing 85 percent by weight of this compound contains, which according to British Patent 692,547 by epoxidizing the above mentioned hexahydro-endo compound is produced.

1,2,3,4,10,10-HeXaChIOr-M ^ a ₁ S ₁ S ₁ Sa-hexahydroendo-1,4-endo-5,8-dimethylene naphthalene, a compound which forms the Diels-Alder adduct Cyclopentadiene and l, 2,3,4,7,7-hexachlorobicyclo- (2.2, l) -2,5-heptadiene, and that obtainable therefrom by epoxidation

1,2,3,4,10,10 - hexachlor - 6,7 - epoxy -1,4,4 a, 5,6,7,8, 8 a - octahydro-endo-M-endo-SjS-dimethylene naphthalene (see British Patent 714,688).

Other chlorinated polycarbocyclic compounds used in the present invention are compounds produced by a Diels-Alder reaction between hexachlorocyclopentadiene and polycyclopentadiene and which have the general formula

Cl

U ^CHs

Cl-C

Cl

Cl-C-Cl! j CH ₂

\ i

i ^x c

XH-;

' ^CH \ i

Cl

XH

exhibit. In this formula, η = 1 or more. This group also includes the compounds which can be prepared by a Diels-Alder reaction between one or two times the molecular amount of hexachlorocyclopentadiene and a molar proportion of naphthalene, anthracene or other such unsaturated, carbocyclic compounds. Compounds of this type are described in British Patent 730,430.

Compounds according to the invention of type I and II, in which R ₁ and R ₂ together form part of a heterocyclic or polyheterocyclic ring system, can, for. B. contain oxygen, sulfur or nitrogen in the ring system. Examples of such compounds are the Diels-Alder adducts of hexachlorocyclopentadiene and dihydrofuran or

7c other compounds, e.g. those with the following

Formula (in which Y is hydrogen or an alkyl radical means):

Cl

Cl CI XH- CY ₂ - O ^

I Cl-C-Cl I, S: O

Cl-C j CH-CY ₂ -CT C

Cl

Although the aforementioned chlorine compounds are preferred to the corresponding bromine compounds, because they are cheaper to manufacture, compounds can also be used in the context of the invention containing bromine or bromine and chlorine. An example of such a compound that according to the invention can be used is the Diels-Alder adduct of hexabromocyclopentadiene and cyclopentadiene.

According to the invention, the 2,3-dihydro derivatives of the compounds described above can also be used will. An example of this is dichloro- (7,7) -endomethylene-l ^ .S ^ -tetrachlorocyclohexane.

Other derivatives, such as epoxy, episulphide, episulphoxide, episulphone, ethyleneimine or halogenated Derivatives of the compounds described above can also be used. examples for such halogenated derivatives are the compounds described in British Patent 618,432, which by halogenating a Diels-Alder adduct of a hexahalogencyclopentadiene and a conjugated diolefin can be obtained.

Some of the compounds that can be used as extreme pressure additives within the meaning of the invention, are already known as insecticides and e.g. in German Patent 945 448 and in Swiss patents 295 916 and 299 283 have been described,

Hexachlorocyclopentadiene can also be reacted under various conditions "with TrichlorätÜylen, with high yields either of a compound with the empirical formula C ₇ HCl ₉ such as 5- (1,2,2,2-tetrachloroethyl) pentachlorocyclopentadiene or of a chlorocarbon with the empirical Formula C ₇ Cl _8. If the reaction between the trichlorethylene and the hexachlorocyclopentadiene is carried out, for example, in the presence of aluminum chloride at higher temperatures, for example 110 ° C., octachloro-1- or -2-vinylcyclopentadiene is obtained as reaction products which do not have the structure of a Diels-Alder adduct, but are nevertheless suitable for use in the context of the present invention. The dimer of hexachlorocyclopentadiene preferably used can be prepared by heating hexachlorocyclopentadiene with aluminum chloride at 75 to 98 ° C. for several hours, if desired with the addition of a chlorinated hydrocarbon solution like carbon tetrachloride.

The connection is a white, solid body that is placed in a closed tube at 480 to 490 ° C melts. The preparation of the dimer is described by H. J; Prins in Rec. Trav. Chim., 65, p. 455 (1946), described.

Derivatives of such reaction products can also 'im. .Frame: can be used in the present invention, e.g. B. the "ketone" derivative of the dimer of hexachlorocyclopentadiene. This compound has been described by McBee in the Journal of American Chemical Society, Vol. 78, p. 1511 (1956). It has the empirical formula C ₁₀ Cl ₁₀ O and a melting point of 349 ° C. Neither the dimer itself nor the ketone derivative thereof has a Diels-Alder structure, and due to the lack of a double bond, they do not store any halogens. The exact structure of these compounds is not known; However, Mc Bee, loc. cit., took the view that these compounds have a cage structure that does not contain any carbon-carbon double bonds.

The reaction products mentioned for their production In the context of the present invention, no protection is claimed, are preferably in Concentrations between 0.1 and 5 percent by weight of chlorine are used and especially in quantities between 0.5 and 2 weight percent chlorine based on the weight of the lubricating oil.

The lubricating oil used in the blends of the present invention can be any natural or synthetic oil with lubricating properties. Thus, the oil can be a hydrocarbon oil that comes from paraffinic, naphthenic, midcontinent or coastal crude oil and / or from mixtures of these. The viscosity of these oils can vary over a wide range, e.g. B. from 40 SUS at 100 ⁰ F to 1000 SUS at 210 ° F. The hydrocarbon oils can be polymerized with fatty oils, such as castor oil or lard oil, and / or with synthetic lubricating oils, such as olefins, copolymers of alkylene glycols and alkylene oxides, organic esters, z . B. Di- (2) -äthylhexyl-sebazat, Dinonylsebazat, Dinonyladipat, Dioctylphthalat and Trioctylphos-. phat, polymers! Tetrahydrofuran and polyalkyl silicone polymers, e.g. B; Dimethyl silicone polymers. The synthetic lubricating oils, in particular diester lubricating oils, are preferably used as the sole lubricating oil or in a mixture with fatty oils. In addition, the lubricating oil used can be thickened to the consistency of the lubricating grease by a soap or an inorganic gelling agent.

Mixtures according to the invention preferably additionally contain a small amount of one substance known as a lubricant component that acts as a hydrogen halide acceptor. Suitable connections are those containing an epoxy group. Such compounds can be other than the epoxy group contain no other functional group, such as pinene oxide and propylene oxide, or they may Represent epoxyuminoalkanes, such as l, 2-epoxy-3-aminopropane, or ethers, such as glycidyl vinyl ether, glycidyl ethyl ether, glycidyl phenyl ether and 1,2-epoxy-5-ethoxypentane, or epihalohydrins such as ethyl chlorohydrin and 2,3-epoxy-4-methyl-1-chlorohexane. Polyepoxides, i.e., compounds containing more than one epoxy group can also be used will. It can be monomeric compounds that contain more than one epoxy group, such as vinylcyclohexenedioxide, epoxidized soybean oil, butadiene dioxide, 1,4-bis- (2,3-epoxypropoxy) -benzene, 4,4'-bis- (2,3-epoxybutoxy) -diphenyl ether and 1,2,3,4-tetra- (2-hydrOxy-3,4-epoxybutoxy) butane; or they can also be compounds of the polymeric type. The proportion is preferably in such a connection between 0.3 and 3.0 percent by weight, calculated on the weight of the lubricating oil, and most particularly expediently about 1 percent by weight, calculated on the weight of the lubricating oil.

example 1

The lubricating oil used is a synthetic diester oil composed of 70 percent by weight dinonyl sebacate, 20 percent by weight dioctyl sebacate and 10 percent by weight dinonyl adipate. Samples are prepared by adding the chlorine-containing compounds to be tested to the base esters, so that a concentration of 1 percent by weight of chlorine, calculated on the weight of the lubricating oil, results. IAE gear tests are carried out with base esters plus lÄSAlO.lO-hexachlor-l. ^ A ^ ÄSa-hexahydroendo-1,4-exo-dimethylene naphthalene (additive A) and with base esters plus hexachlorocyclopentadiene and for comparison purposes with the base esters alone and with base ester plus the dioctyl chloroate known from US Pat. No. 2,771,423 as an additive to high-pressure lubricants. The test is performed at 2000 rpm and at 60 ⁰ C. Each oil two tests are carried out using samples of 2.27 1, at a feed rate of 0.28 1 per minute. The results of these tests are summarized in Table I. The results show that the dioctyl chloroate has no beneficial effect on the extreme pressure properties of the base esters, while additive A and hexachlorocyclopentadiene improve the extreme pressure properties of the base esters.

Table I.

Base tester

Base ester + additive A

Base ester + hexachlorocyclopentadiene

Base ester + dioctyl chloroate

Medium

Abrasion load

in kg

26.3
34.0

35.4
22.7

Corresponding tests were carried out with the same base esters with the addition of hexachlorocyclopentadiene and dimethyl chloroate carried out at temperatures of 60 and 100 ° C. The ones from the following Experimental results shown in the table show that the favorable properties of the invention Additives are still present even at higher temperatures, while the diester is insufficient shows technical effect.

Table Ib

Tem
temperature
⁰ C Medium
Abrasion load
in kg
(analogous to example 1] Base ester + chloroic acid f
dimethyl ester -, .. \
Base ester + dimers of f
Hexachlorocyclopentadiene 1 60
110
60
110 22.5
25th
36
45

Example 2

The base esters in this example are the same as described in Example 1.

The I.A.E. gearbox tests mentioned in Example 1 are carried out at different temperatures with base star plus additive A repeatedly and also for comparison purposes with base star alone and with base esters plus dimethyl chlorate. The results of these tests are shown in Table II. The results show that additive A is effective in improving the extreme pressure properties the base ester is more effective than ίο the dimethyl chloroate.

Table II

Tem
temperature
⁰ C Medium
Abrasion exposure
in kg
at
2000 rev / min Base tester < 60
85
110
60
85
110
60
85
110 27.2
25th
22.7
34.0
29.5
27.2
22.7
22.7
25th Base ester + additive A <
Base ester + chloroic acid- J
dimethyl ester I.

Example 3

The base esters in this example are those described in Example 1. Those described in Example 1 I.A.E. transmission tests are carried out at various temperatures with base esters plus 1,2,3,4,10,10-hexachlor - 6,7 - epoxy -1,4,4 a, 5,6,7,8,8 a - octahydro-endole, 4-exo-5,8-dimethylene naphthalm (Additive B) and for comparison purposes with base esters alone and with base ester plus dimethyl chlorate. The results of these tests are shown in Table III. The results show that additive B in the sense of improving the high pressure properties of the base ester more effective than Is dimethyl chlorate. The tests according to this example are carried out at 4000 rev / min. carried out.

Table III

50 Base tester < Tem
temperature
⁰ C Medium
Abrasion load
in kg
at
4000 rev / min 55 [
Base ester + additive B <
Base ester + chloroic acid- I
dimethyl ester 1 60
85
110
60
85
110
60
85
110 11.3
13.6
13.6
34.0
29.5
22.7
22.7
13.6
13.6

Example 4

1.3 percent by weight of dinating hexachlorocyclopentadiene is added to a lubricating oil which consists of 33 percent by weight of a copolymer of ethylene oxide and propylene oxide in a ratio of ^{15:85 and 67 fl} / o of the base ester described in Example 1. There are tests in the transmission according to IAE

carried out in the manner described in Example 1. The results are shown in Table IV.

Table IV Abrasion load
in kg 40.8 Base oil 63.5 Base oil + 1.3% dimer of
Hexachlorocyclopentadiene

Example 5

The dimer of hexachlorocyclopentadiene according to Example 4 is added in various proportions ¹ S to a paraffinic, solvent-extracted petroleum distillate having a Redwood I viscosity of 65 seconds at 60.degree. IAE transmission tests are carried out in the manner described in Example 1. The results are compiled ^{in Table V ao.}

Table V

Base oil

Base oil + 1.3 percent by weight
Dimers of hexachlorocyclopentadiene

Base oil + 2.6 percent by weight
Dimers of hexachlorocyclopentadiene

Abrasion load

in kg temperature ° C

60 I 110

27.2 43.1 58.9

22.7 38.6 61.2

Mixtures according to the invention can contain minor amounts of other known lubricating oil additives, such as antioxidants, anti-wear agents, fining agents, pour point depressants, Viscosity improvers and anti-foaming agents.

Very suitable antioxidants are e.g. B. alkylphenols, aminophenols and amines.

Suitable anti-wear agents include esters of phosphorus-containing acids and neutral ones aromatic sulfur compounds with a relatively high boiling point.

Dimethyl silicone polymer can be mentioned as an example of a suitable anti-foaming agent will.

As further additional components, the new lubricating oils can contain oil-soluble urea or thiourea derivatives, Polyisobutylene polymers and polymerized unsaturated esters from fatty acids and monohydric acids Contain alcohols.

Claims (12)

PATENT CLAIMS: 1. Lubricating oil mixture, consisting of a lubricating oil base and a low content of Hexachlorocyclopentadiene or a reaction product of a cyclopentadienyl compound with the general formula X - C X-C X-X -C-X 65 70 in which X is a hydrogen, chlorine or bromine atom, and an unsaturated compound, the at least one ethylenic or acetylenic bond, but no carboxylic acid, anhydride or Contains ester group and which has at least 1 chlorine atom or bromine atom, provided all X represent hydrogen atoms indicated in the formula. 2. lubricating oil mixture according to claim 1, characterized in that the carbon atoms between which has an ethylenic or acetylenic bond of the unsaturated compound, each carry an organic radical, the organic radicals together part of a carbocyclic, polycarbocyclic, heterocyclic or polyheterocyclic ring system form. 3. lubricating oil mixture according to claim 2, characterized in that the reaction product 1,2,3,4, 10,10 - hexachloro-1,4,4a, 5,8,8a-hexahydro-endol, 4-exo-5,8-dimethylene naphthalene or 1,2,3,4,10, 10 - hexachlor - 1,4,4a, 5,8,8a - hexahydro - endo 1,4-endo-5,8-dimethylene naphthalene is. 4. lubricating oil mixture according to claim 1, characterized in that the reaction product is a Contains epoxy, episulfide, episulfone, episulfoxyd or an ethyleneimine group. 5. lubricating oil mixture according to claim 4, characterized in that the reaction product 1,2,3,4, lO ^ Hho ^ o py hydro-endo-1,4-exo-5,8-dimethylene naphthalene or 1,2,3,4,10,10-hexachlor-6,7-epoxy-1,4,4a, 5,6,7, SjSa-octahydro-endo-l ^ -endo-SjS-dimethylene naphthalene is. 6. lubricating oil mixture according to claim 2, characterized in that the unsaturated compound the general formula X-C Ii x — c- X-X C-X X ₂ -C
XC = CX ₂ CX in which each X can represent a hydrogen, chlorine or bromine atom. 7. lubricating oil mixture according to claim 6, characterized in that the reaction product is the Is dimers of hexachlorocyclopentadiene. 8. lubricating oil mixture according to claim 4, characterized in that the reaction product is the Is a keto derivative of the dimer of hexachlorocyclopentadiene. 9. lubricating oil mixture according to claim 1, characterized in that the reaction product 5- (l, 2, 2,2-tetrachloroethyl) -pentachlorocyclopentadiene, octachlor-1 or octachlor-2-vinylcyclopentadiene is. 10. lubricating oil mixture according to claim 1 to 9, characterized in that the reaction product 909 730/445 is present in a concentration equal to 0.1 to 5 percent by weight chlorine, calculated on weight of the lubricating oil. 11. lubricating oil mixture according to claim 1 to 10, characterized in that it is an oil base contains synthetic lubricating oil such as a synthetic diester lubricating oil. 12. Lubricating oil mixture according to claim 1 to 11, characterized in that there is still a minor amount of a monomer known as a lubricant ingredient, one or compound containing several epoxy groups or a polyepoxide, e.g. B. glycidyl vinyl ether, contains. Considered publications:
U.S. Patents Nos. 2,622,096, 2,771,423,
832. © 909 730/445 2.60