DE1594571A1 - Lubricating oil suitable as gear oil - Google Patents

Description

P 7222 J / F

SHELL INTERUAl ¹ IONALE RESEARCH MAATSCHAPPIJ NV, The Hague /

Netherlands

"Lubricating oil suitable as gear oil"

Priority! March 6, 1964 / USA registration no .: 350 105

I) The present invention relates to a lubricating oil, which is particularly suitable as a gear oil.

It is well known that the most effective and also economically cheapest additives for gear oils consist of a mixture of lead naphthenate and a sulphurized fatty oil.

009820/14 * 1

splelswelse steel rolling mills and power generation plants been used. However, the recently used operating conditions lead to rapid oxidation of a such gear oil, a sludge formation as well as a co-precipitation of the additives, whereby the oil in the latter impoverished, as well as a general breakdown of the gear oil, so that the systems concerned suffer severe damage, increased repair costs are expended must and an undesirable loss of time and loss of production occurs.

It has now been found that a mixture of a bright stick and a mineral lubricating oil with a high viscosity index is an excellent carrier medium for a lead salt of a carboxylic acid and a sulphurized fatty oil and that in this way the service life of such an additional mixture is calibrated can be increased significantly even at extremely high pressures. It has also been found that this base oil blend It is no longer absolutely necessary to use the fatty oil, although better printing properties can be achieved if a sulphurized fatty oil is also present.

Accordingly, the invention relates to a special al Gear oil 'suitable lubricating oil, which consists of a mixture

009828/1411

6AD ORIGINAL

a bright stock oil and a mineral lubricating oil with each with a viscosity index of at least 80 and a lead salt of a carboxylic acid, preferably lead naphthenate, and optionally a sulphurized fatty oil.

If sulphurized fatty oil is not used, you can the gear oil according to the invention at 25-90 wt .- # from the bright stock, at 5-70 wt .- # from the lubricating oil and at 1.-15 wt .- ^ consist of the lead salt, each related on the finished overall mixture. If, on the other hand, a fatty oil is also used, the composition according to the invention can for 55 - 85 Vol .- # from the Bright Stock, for 45 15 Vol .- ^ from the mineral oil as well as 1 - 10 and preferably to 2 - 5 Vo1 .- $ from the. Lead salt, based on the oil mixture, and from 1 to 10 vol .- #, preferably from 3 to 6 vol .- # the fatty oil, also based on the volume of the oil mixture.

"Bright stock" is understood to mean a raffinate which one during the refining of mineral oils from the so-called short residue after separating the distillate fr actions received. The short residue is dewaxed and deasphalted and, if desired, trapped with a solvent and fuller's earth treated, the raffinate being obtained as the end product.

009828/1461

M3 ORIGlNAt

In the absence of a sulphurized fatty oil, the Bright Stock can have a viscosity of at least 500 Redwood I seconds at 60 °. If, on the other hand, sulphurized fatty oil is also used, the bright stock can have a viscosity of more than 1,250 SUS at 37.8 ° and preferably from 1,500 to 3,500 SUS at 37.8 °. In any case, the bright stock can have a viscosity index of 90-110 and contain at least 5%, preferably 5-70%, of aromatics.

The properties are shown in Tables I-III below specified by certain bright stock types, soft im The scope of the invention is of interest

T ABELLB

Properties of Bright Stock Types

Viscosity, SUS, 37 _t 8 ^c

Viscosity, SUS, 98.9

Viscosity index ⁰ Q
⁰ O Aninil point ⁰ G 600 Flash point,
Focus, Percent aromatics
^{! l} naphthenes 828 / Stook point j m

'Peraffin

> 125O, generally 1250 - 11000,

preferably 1500 - 3500> 75 »generally $ 12 - 325,

preferably 150-250> +80, preferably +65-110 > 100, pre-approved> 115. > 246, precautionary white > 260 '> 288, preferably> 325 -D <? Mm ^ lKua "anticipated" lower as »9s4

60

OFiIGlNAL

TABLE II Examples of typical bright stock types according to gabeile I

Mid-Continent-Bright-Stock Penneylvania-

Bright floor

Hilde Extraction Sharp

extraction

Viscosity, SUS *, 37.8 ° 2 569 * 9 2,049 2 109 Viscosity, SUS, 98.9 ° 141 19th 131 144 Viscosity index 85 72 • 95 102 Ring analysis Aromatics 5.8 5 5 Naphthenes 685 19th 16 Paraffins 76 79 Ratio of paraffins 3.4 to naphthenes 5.62 4.95 Average molecular weight 675 730 Medium number of rings per mole 2.9 5.0

SABBLLE IXI

Rules for typical Mld-Continent-Bright-Stock types

(Table I)

Seventh, ⁰ API, minimum
Color, NPA

Stookpunlct, ⁰ O, maximum flash point, ⁰ C ₉ minimum fire point, ⁰ G, minimum viscosity, SUS * SB »^ *

infiltrated Filtered 25.5 24.5 25.5 6+ dark green 6.7 -12.2 -12.2 -12.2 282 305 285 324 346 321 150-170 200-215 150-160

Q i '■

BATH ORIGINAL

In the absence of a sulphurized fatty oil, the mineral lubricating oil can have a viscosity of 50 - 700 Hedwood I seconds at 60 °. If, on the other hand, a sulphurized fatty oil is present, the mineral lubricating oil can have a viscosity of 100 - 600 SUS at 37.8 °. Can in both cases the Mineralschaieröl a Viekosltäteindex 90-110 and 2 comprise - preferably containing 10 i "heterocyclic aromatics in the form of sulfur-containing aromatics. Examples of such sulfur-containing aromatics are benzothiophenes, dibenzothiophenes, tbiophenacenaphthylenes, thiophenophenanthrenes and thiophenopyrene. _k

• ·

A suitable mineral grade, which is hereinafter referred to as For example, "fraction Y" can be denoted from an East Texas crude oil and has the following properties

Viscosity SUS, 37.8 ° 250 ViekoeitatBinde * 90-95

Analysis (incrementa of Ultraviolet absorption)

14 ^ mono aromatics *

21 56 poly ar 0 mats of which 13 - 17 ϊ

Diaromatics with thiophene structures, e. G. Benzo- and dibensothiophenes.

original

Mixture A

Mixture B

5io resins with polar groups »the heat consists essentially of saturated compounds. Preferred semi-marriages produced using this fraction Y are

60 Vol .- * Bright Stock (Unfiltered - Table III) 40 vol .- # fraction Y. 70 Vol.-9t Bright Stock (12 * aromatics) 30 Vol.-j6 Fraction Y

The lead salt of a carboxylic acid can be produced from naphthenic acids which are obtained in the hafi kidney of petroleum, with the naphthenic acids obtained from lubricating oil fractions being particularly suitable for the purposes of the invention. These naphthenic acids can also be up to 30 % or more Contain non-saponifiable mineral oil. A typical beinaphthenate, which has been produced from haphthenic acids of a lubricating oil with a non-dispensable proportion of about 23 pounds, has, for example, a PbO content of about 20% by weight. In contrast, a sleinaphthenate which was produced from naphthenic acids, which are essentially free of non-saponifiable constituents, has a PbO content of about £ 50. The lead core in question is preferably basic. lii & i increase in Baeizität of Bleisalces can lead to an improvement% u ien Höchstdruckeigensohaften the finished oil · -

009823 / UÖ1

ORIGINAL BATHROOM *

A3 * sulfurized fatty oil is preferably a sulfurized ester of a fatty acid with a sulfur content of 10-40 # used. In such esters may be, for sulfurized sperm oil with a sulfur content of 20 20 i>. Mn such sulfurized oil is commercially available under the names "Base 10Ö-S" or "Base 120-S ¹¹ and is manufactured and sold, for example, by Carlisle Chemical Works. The sulfurized oil with the name" Base 120-S "has the following properties»

sulfur

Sperm oil

API density at 15 «6 ° Lbs / gal at 15 ° (0.082 kg / liter) pour point, ASXIi flash point, COC fire point, COO unsaponifiables AOCS viscosity at 98.9 °, 3US corrosion, ASIM color, ASTM (2 - 1/4 * Solution) solubility

Schwefelaueeehtiäuog

13.0 1 » 87.0 t

14.88.05

18.3 ° 229.4 ° 257.2 °

35 36 250

positive 4

in practically all oils completely löalioh no «

009828 / Uei

bath

A small proportion of a further additive can also be present in the cream mixes according to the invention. Examples of such additives are polyolefinic connecting agents with a molecular weight of 800-2000, such as polybutenes, polyisobutylenes or alkylated naphthalenes, which can be used in amounts of 1-5%; Furthermore, foam inhibitors, such as polymeric simethylsilicones with a viscosity of 100-1000 cS and preferably 200-300 cS at 25 °, as well as antioxidants in amounts of 1-5 & ew .- #, (for example alkylphenols (e.g. Si and trialkylphenols, such as 2 , 4-, 2,3- », 3,4-, 2,6- and 3,5-siaaylpbenolj 2 _t 4-simethyl-6-tert-butylphenol} 2,4-di-tert-butyl-4-methylphenol ), bisphenols (eg 4.4 * methylene (2,6-di-tert «butylphenol)} 4.4 ^l -thio-bis (2 _p 6-di-t>utylph" nol)) and aryl amines (e. g. Phθnyl-alpha-naphth bylaain and phenyl-beta ~ naphthyla * in)).

The invention is further illustrated by the following examples explains what the composition of τοη gear oils indicate »how they are often claimed ·

009828/1481 bad original

Example I. - 10 - ■ Blelnaph 1594571 tnenat Ferti Brigbt stick mineral oil Wt total oil with a with a Baicity Viscosity Viscose of lead index over activity index naphthenate 80 and one over 80 Gew ~ i ° viscosity and one from 650 ßed- viscosity - wood I, Se from 650 customers at Redwood I 4.7 60 °, wt . Seconds
at 60 °, 5.0 a 27.5 67.8 5 * 0 b 27.0 68.0 5.0 '52.5 0 85.0 10.0 10.0 52.5 d 88.5 6.5 10.0 52.5 β 28.0 62.0 5 * 0 52.5 f 88.0 2.0 5.0 . 52.5 β 27.5 67.5 52.5 H 65.0 10.0 55.0 55.0

BtiBPiel II Mieohung A + 2.7 Vol.-i Bltinaphthtnat, be «og« n on da ·

Oeaieoto aue Bricht-Stook and fraction Y

4-4 vol Jt geeolmefelt · "Sp" ZA01 (15 j S).

otsogtn on daa Cfoaieofc mm Bri «ht-Stock and Fraction T

000828/14 · 1

SAO

+ 1 vol. £ polyisobutylene (MW 1200),

based on the mixture of bright stock and fraction I.

+ 5 parts per million dimethyl silicone polymer (200 cS at 25 0), based on the G-emic Bright Stock and Fraction Y

Example III

Mixture B + 2.7 Vol.-?

+ 4.0 vol. + 1 vol. -9 +

Blelnaphthenate, based on that Mixture of Bright Stock and Fraction Y

sulphurized sperm oil (13 # S), based on the mixture of Bright Stock and Fraction Y

Polyisobutylene (MW 1200), based on the mixture of Bright Stock UDd parliamentary group Y

Parts per million dimethyl silicone polymer (200 cS at 25 C), based on the mixture from Bright Stock and fraction Y

Example IV

Mixture A + 3 * 0 vol. -56 lead phosphorus, based on the

Mixture of Bright Stock and Fraction Y

+ 4 * 5 vol. -36 sulphurized sperm oil, based on the mixture of bright stock and fraction ϊ

O
(O
OD

Example ?

65 YoI .-

35 VoI -

Bright Stock (40 36 aromatics)
HVI Mineralscbraieröl (VI '90 aromatics 55 f>

+ 4 Vol .- # lead naphthiate, based on that

Mixture auo bright-stock and fraction Y

+ 4 % by volume of sulphurized semen oil, based on the mixture of Bright-Stock and

Fraction Y

BATH ORIGINAL

Example VI

Vol .-? 6 Bright-Stock (50 # aromatics)

Vol.-36 HVI mineral lubricating oil (V. I. »90, aromatics 30 #)

+ 2.5-Vol.-56 lead naphthenate, based on the

Mixture of Bright Stock and Fraction Y

+ 4 vol .- # of sulphurized semen oil “based on the mix of Bright-Stock and. Fraction Y

Example VII

Mixture A + 2.7 VoI * - ^ lead naphthenate, based on the

Mixture of Bright Stock and Fraction Y

+ 4.0 vol .- # of sulphurized sperm oil (13 1 · S), based on the mixture of bright stock and fraction Y

+ 1 vol .- # polyisobutylene (MW 1200), based on the mixture of bright stock and fraction Y

+ 1 vol. -56 polyisobutylene (MW 800), based on the mixture of bright stock and fraction Y _o

+ 5 ropes per million diaethyleilioonpolymer (200 cS at 25 ⁰ Cj

Some of the above-described oil blends, identified by the number dee Examples, as well as oils which do not fall within the scope of the invention, were subjected to some tests, the results obtained being summarized in Table IV below.

009828 / U81

(X) 148.9 ° - Benoh Oxidation Test

In this test method, 300 ml of the oil in question are added to a cylindrical glass cell made of Pyrex glass 148.9 ° with passage of 5 liters of air for an hour oxidized for a total of 168 hours. A catalyst is there not present. The relative resistance to oxidation Oil results from the increase in viscosity and the ski education during the test.

(XX) Modified turbine oil stability ateate This test is a modification of ASTM method D-943 "Oxidation Characteristics of Inhibited Steam Turbine OUi". The modification consisted in the fact that the test temperature was increased from 6.1 ° to 121.1 °, that air was used instead of oxygen and that no water was present of the oxidation condition, which is required to double the initial south-over-temperature at 98.9 °

The Zeat method was used to test the corriditrea- & en attack on copper at 100 ^c bu. The method was also modified to avoid the corrosive attack

009828 / U81

BAD ORJG1NAL

of the oil mixtures on copper and steel (AISI 1020) 148.9 ° to be able to check. The appearance of the metal strips after a three-hour immersion treatment with the person concerned Test temperature is used to detect the corrosive Evaluate properties of the tested oil.

00982371481

co *. ^

TABLE IV

Percent
tuale
increase
the SUS
Viscose
activity by-
98.9 ° • (X)
mud
¹ JiIdUiIg
at Ver
search
de in mg Lead-
ver
desire
in -. - (XX)
mud
education
in mg each
10 g of oil - 159A571 (XlGi)
Possibly
liche '
maxi
times
Bela
stung
in kg (XXXX
Ou-Ko:
ro si o:
at 1i
and
148.9 Finished oil 510 56 20th 04/24 Ka) 19th 40 18th 28.12 Kb) 35 15th 29.84 Kc) 100 347 25.86 Kd) 83 • 419 27.22 Ke) - ...! ' ■ 04/24 Kf) ■ ***> ■ .. '.
m 27.22 Kg) 820 26.31 Kb) 7.6 76 27.22-29.48 beat II 8th 50 27.22-29.48 η III 7.5 .45 27.22-29.48 η VII 48.8 '409 20.41 Vere 60/40 mixture
from steam.
finished earth -
oil + mineral
lubricating oil (40
Yi sko si tat sj .n-
dec) with Zv.satz-
mixture vc.n II 38.2 277 20.41 Tare Bright-Stock +
nineralachmler-
Ul (40 viscosi
ity Bi-Ad ex) with
Zueacsgemiech
Tone III . he · »IT mhm-r with - _: - —- ■ Λν
ί
if.34 τοπ H i> iJL tU * t ΜΛΛ. H
anatelle of
Blelnaphtbenat
In equal -
kill * *
24.95
I. verc Like II, but bit
Di benzyIdIsulphide
instead of
acbwefeltem spur
oil in equal
amounts
•

009828 / UI1

BATHROOM OPIGiMAL

Claims (27)

PATENT CLAIMS 1) Lubricating oil which sioh in particular suitable as a gear oil, characterized in that it consists of a mixture of a bright stock and a mineral lubricating oil, each with a viscosity index of at least 80. as well as a lead salt of a carboxylic acid 2) lubricating oil according to claim 1, characterized in that it is 25 - 90 wt .- ^ from the bright stock, 5 - 70 wt .- ^ from the mineral oil and 1 - 15 wt .-% consists of the lead salt of a carboxylic acid, in each case based on the finished Gesamtnieohung. 3) Scbnierul according to claim 1 or 2, characterized characterized in that ea contains a bright stock with a viscosity of at least 500 Redwood I seconds at 60 °. A) Soaking oil according to claims 1 - 3 _f, characterized in that it contains a bright stook with an sindex viscosity of 90 - 110. 5) lubricating oil according to claims 1-4, characterized in that the bright stook has a content of at least 5 i » of aromatics. BAD ORJGiNAL 003829 / USI 6) Lubricating oil according to claim 6, characterized in that the bright stock has a content of 5-70 i » of aromatics. 7) Lubricating oil according to claims 1 - 6, characterized in that it contains a mineral lubricating oil with a quality of 50 - 700 Redwood! »Seconds at 60 °. 8) Lubricating oil according to claims 1-7, thereby characterized in that it contains a mineral lubricating oil with a viscosity index of 90-110. 9) lubricating oil according to claims 1-8, characterized known that <äae Mineralechtoleröl «in a proportion of Contains 2 - 10 pounds of heterocyclic aromatics. 10) lubricating oil according to claim 9, characterized in that the Hineralsohnler oil contains eohulfur-containing aromatics. ■ ■ ■ · · ■ · 11), Sohaiitröl according to Anepruob 1-10 »thereby this contains tin baaiech · «lead al *. 12). Switching oil according to claim 1-11, daduroh It is worth it that it contains blinaphth * nate. eomt / 1411 13) lubricating oil according to Anapruch 1, characterized that there is also a sulphurized fatty oil contains. 14) A lubricating oil according to claim 13 'characterized in that it contains as fatty oil a sulfurized ester of a fatty Deesen sulfur 10-40 weight is 56. 15) Lubricating oil according to Anepruoh 16, characterized in that it contains a sulphurized sperm oil with a sulfur content of 20-30% by weight, based on the sulfurized oil. 16) lubricating oil naoh claim 13-15, characterized in that it consists of a mixture of 55-85 vol. -J * of a bright stock and 45-15 vol and 1 - 10 Vol.- £ of a sulphurized fatty oil, each based on the volume of the mixture of bright stock and mineral oil. 17) Sohmieröl naoh Anepruoh 13-16, daduroh characterized that et contains a Bright-Stook with a viscosity over 1,250 SUS at 37.0 ° . 009828 / US1 18) Lubricating oil according to claim 17, characterized »that it contains a bright stock with a viscosity of 1500 - 3500 SUS at 37.8 °. 19) lubricating oil according to claim 13-18, characterized characterized in that it contains a bright stock with a viscosity sindex of 90-110. ' 20) Lubricating oil according to claims 13-19 *, characterized in that the bright stock contains an aromatic content of at least 5 % 21) A lubricating oil according to claim 20, characterized in that the Bright StoQk an aromatics content of 5 - 70 contains f>. 22) lubricating oil according to claim 13-21, characterized characterized in that it contains a mineral lubricating oil with a viscosity of 100 - 600 SUS at 37.8 ° t 23). Lubricating oil according to claims 13-22, characterized in that it contains a mineral oil with a quality index of 90-110. 009828/1481 BADORiGiNAL «20 - 24) Schmievöl according to claim 15-23, characterized marked that the idtneralschmleröl has a salary of 2 - 10 ^ of heterocyclic aromatics contains. 25) lubricating oil according to claim 24 »characterized in that that the mineral lubricating oil contains sulphurous aromatics. 26) Lubricating oil according to claims 13-25 »characterized in that it contains a basic lead salt · 27) lubricating oil according to claim 26, characterized in that it contains lead naphthenate. 009828 / Uei