DE1234905B - Lubricating oil - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL: ClOm

C 10 M 169 / OOB4 2

German class: 23 c-1/01

Number: 1234 905

File number: S 77241IV c / 23 c

Filing date: December 21, 1961

Opened on: February 23, 1967

If · 'J / O.

The high pressure that occurs with certain types of gears and bearings can tear the lubricating oil film with resulting damage to the machine. It is known per se that by Adding certain substances to lubricating oils can be improved, so that excessive wear, chafing and cracking can be minimized or completely prevented.

Suitable known extreme pressure additives are certain compounds of metal reactive compounds Elements such as chlorine, sulfur and phosphorus, and also z. B. some lead compounds. Particularly Noteworthy among the additives used so far are the lead soaps, phosphoric acid esters, freer or bound sulfur and certain chlorinated organic compounds. A major disadvantage of many of these high pressure additive mixtures is their generally strong reactivity to the Metal surface, causing etching, corrosion and discoloration of the metal surface. Another The disadvantage is that they change the original chemical nature of the contact surfaces. aside from that are additives of this type because of their reactivity in general quickly ineffective, so that so only a short-term lubrication is achieved.

According to one proposal, oil-soluble thioether derivatives are used as improved extreme pressure additives an ester of a long chain unsaturated fatty acid and a polyoxyalkylene diol or its sulfur analogs are used.

Lubricating oil

Applicant:

Shell Internationale Research Maatschappij N.V., The Hague

Representative:

Dr. E. Jung, patent attorney,

Munich 23, Siegesstr. 26th

Named as inventor:
George Milton Calhoun,
Berkeley, CaUf. (V. St. A.)

Claimed priority:
V. St. v. America December 23, 1960
(77781)

It has now been shown that these disadvantages are avoided if a lubricating oil is 0.05 to 20 percent by weight of a thioether derivative of the general formula

Z - (CHOn - SO - R - COO - (R ² - X) _x - (R ¹ - O) ₂ , - CO · R - SO - (CH ₂ ) ^ - Z

in which R is a long-chain hydrocarbon radical, optionally containing hydroxyl groups, X is oxygen or - SO -, R ¹ and R ^{2 are} identical or different alkyl radicals with 2 to 8 carbon atoms, Z = OR ³ or COOR ³ , where R ^{3 is} hydrogen or a C ₁ - to C ₄ -alkyl radical, χ and y are integers from 1 to 6 and η is an integer from 1 to 4 and optionally 0.05 to 20 percent by weight of a thiaalkylphosphonic compound or its sulfoxy derivative of the general formula

R ₁ X

! +
R __ s - CH - p '

or various hydrocarbon radicals or an alkylamine group, preferably a tert. Alkylamine group with 8 to 24 carbon atoms or a mono- or polyvalent metal and X oxygen or Sulfur is contains.

These compounds are preferably obtained by reacting an ester from a long-chain unsaturated fatty acid with the formula RCOOH, in which R is an unsaturated long-chain hydrocarbon radical which may also contain hydroxyl groups, and a polyoxyalkylene diol or its sulfur analog of the general formula

HO - (R ² - X) _x - (R ¹ - O) y - H

XR ₈

in which R ¹ , R ^a , X, χ and y have the meaning given above, with a mercapto connection

in which R is a hydrocarbon radical with at least manure, e.g. B. a mercapto acid, a mercapto-6 carbon atoms, R ₁ hydrogen or the same alcohol or ether or ester, so that the end product

709 510/512

3 4

at least one and preferably two thioethers are performic acid, peracetic acid and

trichloroperacetic acid remains the most effective; the per-

S (CH ₂ ) tt formic acid and peracetic acid are preferred.

The peracids can either as such or as well

has, the meaning of Z already being used above in statu nascendi. Instead of the

has been specified and subsequent treatment concerned intermediates with an already

to treat with hydrogen peroxide or a percarboxylic acid, formed organic peracid, can

whereby the sulfur atoms in sulfoxide groups are also obtained with a mixture of the

being transformed. treat organic acid and hydrogen peroxide,

The unsaturated fatty acid esters of polyalkylene io with these reagents in stoichiometric proportions

glycol can be used with the formula; in general one takes

Rron cat -> o iMi n \ orR ^{But the acid in excess}

KCUU- (K -x ^ - (K -U) „- ulk _Dk reaction components must be stirred well

are made by esterifying a long chain to ensure intimate contact;

unsaturated fatty acids, such as oleic acid, linoleic, linolenic, 15 with good stirring, the reaction is generally in

Erucic acid, ricinoleic acid, completed with a polyoxyalkylene diol for a period of 30 to 120 minutes,

or the thio derivative thereof such as diethylene glycol, a convenient method for making the

Triethylene glycol, tetraethylene glycol, dipropylene glycol treatment is the mixing of a thioether ester

kol, tripropylene glycol, dibutylene glycol, 2,2'-thio compound with the necessary proportion of the aqueous

diethanol, 3,3'-thiodipropanol. 20 hydrogen peroxide solution and with the organic

Suitable mercapto compounds for the umic acid. The hydrogen peroxide solution is

Substitution with these fatty acid esters are aliphatic moderately used in the form in which they

Mercaptocarboxylic acids, e.g. B. mercaptoacetic acid, is readily available, for example with

Mercaptopropionic acid, mercaptobutyric acid or 100 percent by volume H ₂ O ₂ , corresponding to 30% by weight

Mercaptoalkanols, such as 2-mercaptoethanol, 2- and 25 percent H ₂ O ₂ . It is also expediently

3-mercaptopropanol, 2-, 3- and 4-mercaptobutanol the organic acid used in the form in

or ethers of the mercapto alcohols mentioned, such as which they are commercially available. For example,

2-mercaptoethenyl, methyl or octyl ethers, as well as formic acid in a concentration of

Mercaptoesters such as ethyl mercaptoacetate or ethyl 90 percent by volume H COOH are used, while

mercaptobutyrate and mixtures of such substances. 30 the acetic acid is rendered in the form of glacial acetic acid

This does not yet contain sulfoxide groups. More dilute aqueous ones can also be used

Compounds can be used according to those of K o e η i g and solutions of formic acid, such as

Employees in the Journal of the American Chemical have those with 20 to 50 percent by volume H · COOH. in the

Society, 79 (1957), p. 362 or Fitzgerald in the case of solid organic acids such as trichloroacetic acid,

Journal of Organic Chemistry, 22 (1957), p. 197 35 can be the same in a suitable solvent,

methods described are produced. Preferred such as water or a low-boiling alcohol,

wisely, the reaction will dissolve at low temperatures before adding it to the thioether ester compound

between room temperature and about 50 ⁰ C in an additive and the hydrogen peroxide solution is added. the

Essence of a free radical-forming catalyst, but solid organic acids can also be used before

such as azo or peroxide catalysts or under the mixing and reaction of the components with one another

Exposure to ultraviolet light in one another not dissolved or in the hydrogen peroxide solution

reacting solvents such as benzene, toluene, are dispersed.

Xylene. The following examples explain the manufacturing

The thioether derivatives can be made from these intermediate additives according to the invention, but for what

Products made by treatment with 45 are not claimed within the scope of the invention

an inorganic acid and an aqueous solution.

of hydrogen peroxide or with a percarboxylic acid B ice D ie 1 1
at a temperature between 0 and 100 ° C, preferably at room temperature. a) Approximately 600 g of diethylene glycol dioleate and

Aqueous 50 223.5 g of mercaptoacetic acid can be added to a flask to carry out the treatment

Solutions of hydrogen peroxide used are mixed at 20 to 25 ° C. Over the course of 2 hours

the H ₈ O ₈ in a concentration of 5 to 95 weight- will be about 240 drops (30 drops each on

percent included. As a rule, water is used once) tert-butyl hydroperoxide is added and the

Peroxide solutions with a content of 25 to temperature kept at about 37 "C.

85 percent by weight H ₂ O ₂ , preferably those with 55 The reaction mixture is mixed with 2 volumes of diethyl

30 to 50 percent by weight H ₂ O ₂ . ether diluted, washed with 121 water and on

Suitable inorganic acids are hydrochloric acid, adjusted to pH _{4, dried over Na 2} SO 4, sulfuric acid and phosphoric acid; they are expedient net and nitrided and the solvent was removed at 155 ⁰ C and suitably used in the concentration in 2 mm pressure. The end product is one that is usually commercially available. A mixture of the 9- and 10-carboxymethylmercapto-Man usually prefers acids in the relatively stearate diester of diethylene glycol.
high concentration. Suitable percarboxylic acids are b) About 1 mole of this mixture is mixed with a peracids of the lower fatty acids, such as perform iron-equivalent amount of a solution of hydrochloric acid, peracetic acid, perpropionic acid and perbutter peroxide and acetic acid and acid, the peracids of the substituted lower fat, for 24 hours - Stirred for 65 at room temperature. The sulfoxide product trichloroperacetic acid obtained by acids such as monochloroperacetic acid and extraction with ether, as well as the peracid of the aroma- is a mixture of the 9- and 10-carboxymethylsulfoxytic carboxylic acids, such as perbenzoic acid. From stearate diester of diethylene glycol. The product is in

Oil soluble and has excellent high pressure properties.

Example 2

According to the procedure of Example 1, starting from triethylene glycol dioleate, mercaptoacetic acid, Hydrogen peroxide and acetic acid, a mixture of the 9- and 10-carboxyniethylsulfoxystearate diesters made of triethylene glycol.

Example 3

According to the procedure of Example 1, starting from diethylene glycol diricinoleate, mercaptoacetic acid and peracetic acid, a mixture of the 9- and 10-carboxymethylsulfoxy-12-oxystearate diesters of diethylene glycol manufactured.

Example 4

According to the procedure of Example 1, starting from 2,2'-thiodiethanoldioleate, mercaptoacetic acid, Hydrogen peroxide and acetic acid, a mixture of 2,2'-SuIfoxydiäthanoldi- (9- and 10-carboxymethylsulfoxystearate) manufactured.

The additives according to the invention are oil-soluble, and they can preferably 1 to 5 ° / _0, based on the total weight of the lubricating oil mixture may be used in lubricating oil in proportion amounts of 0.05 to 20%. "

Synthetic oils or natural hydrocarbon oils with a viscosity range of 50 SUS at 37.8 ° C to 250 SUS at 98.9 ° C [the SAE viscosity numbers from SAE 10w up to SAE 90] are very suitable as base oils for the purposes of the invention. Synthetic oils include polymerized olefins, alkylated aromatics, isomerized waxes, and copolymers from alkylene glycols and alkylene oxide, as described in U.S. Patents 2425755, 2425845 and 2,774,733. Are also suitable organic esters of aliphatic dibasic acids, such as. B. Di-2-ethylhexyl sebacate or di-2-ethylhexyl adipate. The mineral oils can be mixed with fatty oils, such as. B. castor oil and bacon oil, and / or with synthetic oil or mixed with silicone polymers. Among the typical oils of this type include engine lubricating oils obtained from petroleum, which are either (A) paraffinic in character or (B) have naphthenic character and have the following properties:

Pour point, ⁰ C

Flash point, ⁰ C

Viscosity; SUS at 98.9 ° C
Viscosity index

(A)
(SAE 1Ow)

-23.3

198.9

44

90

(B)
(SAE 30)

-20.6

212.8

58

60

Other suitable oils are the gas turbine lubricating oils with the following properties:

Flash point, ⁰ C

Pour point, ⁰ C

Viscosity; SUS at 37.8 ° C

Neutralization number

ash

1010

148.9

-23.3

59.4

0.02

no

1065

240.6
-17.8
530

0.01
none The following compositions are characteristic of the invention, the percentages given being based on weight:

Composition A

Additive according to example 1 2%

Mineral oil 1010 98 ° / ₀

Composition B

Additive according to Example 2 2%

Mineral oil 1010 98 ⁹ / "

Composition C

An additive according to Example 3 2 ° / ₀

Mineral oil 1010 98 ° / ₀

Composition D

Additive according to Example 2 1 ° / ₀

Mineral oil SAE 30 99 ¹ Y ₀

Composition E

An additive according to Example 4 2 ° / ₀

Mineral oil ¹ SAE 90 98 ° / ₀

Composition F

Additive according to example 1 2%

Lauric acid 2%

Mineral oil SAE 90 96 ° / ₀

Composition G

Additive according to Example 1 5%

Polyethylene propylene glycol with a viscosity of 660SUS at 37.8 ° C .. 95%

Composition H

Additive according to example 1 2%

Di-2-ethylhexyl sebacate 98 ° / ₀

The evaluation of the lubricants according to the invention with regard to their extreme pressure properties is carried out using a spur gear testing machine (Lubricating Engineering, January-February issue 1956). These The machine essentially consists of two geometrically identical pairs of spur gears, which are separated by two parallel shafts are connected to each other. The gear pairs are located in separate Gear box, which also contains the ball bearings for the storage of the shafts. The one of the waves consists of two sections that are connected to each other by a coupling. The load takes place in such that one side of the coupling is firmly clamped and the other side of the coupling is on Allow torque to act. The test conditions are as follows:

Speed 3200 rev./min.

oil temperature 100 ⁰ C

Flow rate of the oil 10 ml / second gradually increasing

Load in each case in the long run

of 5 minutes

The test results are summarized in the table below. For comparison purposes are also the results when using the base oil alone and when using other known extreme pressure lubricants specified.

Composition of the lubricating oil

Mixture A, B, C and D

Mineral oil 1010 + 2% C _ie -alkenyl-

succinic acid

Mineral oil 1010 4- 2 ° / ₀ Malonic acid ...
Mineral oil 1010 + 2 ° / ₀ 3-hexa-

decyladipic acid

Mineral oil 1010 + 2 ° / ₀ dodecyl-

mercaptosuccinic acid

Mineral oil 1010 + 10 ° / ₀ glycerine

monooleat

Mineral oil 1010 + 2% C ₁₃ H ₂₇ OH

(Oxo process)

Mineral oil 1010

load

upon entry

of eating

kg / cm

2160

252
504

252
252
324

108
108

These data show the excellent improvement in the load capacity of the oil which is brought about by the addition of the new thioether derivatives. On the other hand lead conventionally known additives such as malonic acid, succinic acid, 3-Hexadecyladipinsäure and C _ie alkenyl succinic and sulfur-containing compounds which are outside the scope of the invention as the Dodecylmercaptobernsteinsäure, only a low quality improvement of high pressure properties.

In particular, one can see the favorable properties of the lubricating oil mixtures, which the new thioether derivatives contain, further improved by the additional use of 0.05 to 20 percent by weight the 2-thiaalkylphosphonic compound, or its sulfoxy derivative.

The combined addition of both types of additives to lubricating oils not only has a higher effect Resilience under very high pressures, in preventing corrosion and sludge formation but also provides excellent protection against oxidation. Moreover, this develops

to combination of additives have a much higher resistance to degradation than any of the Single components. Lubricating oil blends containing both types of additives are special suitable as a crankcase lubricant for internal combustion engines and as gear oils; you can are used under operating conditions such as particularly high pressures and temperatures and are exposed to oxidation.

The radical R in the phosphonic compound is preferably a straight-chain alkyl radical having 10 to 18 carbon atoms. The radical R _{2 is} preferably a monovalent or polyvalent metal or an amino group, preferably an alkylamine group. Branched-chain primary amino groups, especially tertiary alkylamine groups having 8 to 24 carbon atoms, are preferred.

Claims (1)

Claim: Lubricating oil mixture based on natural or synthetic oils, characterized in that that it is 0.05 to 20 percent by weight of a thioether derivative of the general formula Z - (CH ₂ ) * - SO - R - COO - (R ² - X) _x - (R ¹ - O) _v - CO · R - SO - (CH ₂ ) * - Z in which R is a long-chain hydrocarbon radical, optionally containing hydroxyl groups, X is oxygen or - SO -, R ¹ and R ^{2 are} identical or different alkyl radicals with 2 to 8 hydrocarbons, Z = OR 3 or COOR ³ where R ^{3 is} hydrogen or a C ₁ - to C ₄ - R - S - CH - in which R is a hydrocarbon radical with at least 6 carbon atoms, Rj is hydrogen or a C ₁ - to C ₄ -alkyl radical, R _{2 is} hydrogen or identical or different hydrocarbon radicals, alkyl radical, χ and y are integers from 1 to 6 and η is an integer Number from 1 to 4 and optionally 0.05 to 20 percent by weight of a 2-thiaalkylphosphonic compound or its sulfoxy derivative of the general formula or an alkylamine group, preferably a tertiary alkylamine group having 8 to 24 carbon atoms or a mono- or polyvalent metal and X is oxygen or sulfur. 709 510/512 2.67 © Bundesdruckerei Berlin