DE2312622A1 - LUBRICANTS AND PRE-MIXTURE USED IN ITS MANUFACTURING - Google Patents

Description

;. JVi. :>:: - "*!. *. \ *. V / AITER BC-'Ϊ.

IjJ .. '.' ■ '' .-: ■■ I WOÜ-r '- * ,,. "

ux.iUK.i '.- -Λ. GJL- 'W-WaT ^ IS73

C.23 FRANKr '.- fej Λ: λ <αλΙ Μ-HIGHEST

Our ifr. 13571

Stauffer Chemical Company weatport, Connecticut, V.öt.A.

fixing agent and usable for its manufacture

Premix.

The usual lubricating oils, e.g. mineral oils, are used today in numerous functional fluids with lubricants synthetic esters, whose viscosity and volatility under the operating conditions are superior to the former are. This applies in particular to the field of automobile and aircraft gas turbines, in which the operating conditions for which lubricants are extremely strict.

309841/0808

So far, attempts have been made to meet these strict requirements by using a large number of synthetic esters as basic materials. The use of plastic esters of dicarboxylic acids, for example the use of diesters of adipic acid or sebacic acid, as lubricants in gas turbines has already been proposed. The dialkyl adipate have favorable viscosities at low temperatures, but their viscosity at high temperatures is so low that they can only be used together with relatively large quantities of viscosity improvers. The adipic acid esters also show a very low resistance to oxidation, even when mixed with conventional antioxidants, under normal operating conditions. Finally, the adipic acid dialkyl have a tendency to thermal ^ ^he fall, so that they are not very suitable as a lubricant in gas turbines.

It is therefore an object of the present invention to provide Basic compounds for functional fluids which have all of the favorable properties mentioned. These basic materials are said to be suitable for use in gas turbine lubricants. The invention also seeks to provide from base materials for gas turbine lubricants that have excellent viscosities at low and high temperatures have, which can also be combined with known antioxidants and masses of exceptional thermal and oxidative resistance, and which can still be produced relatively cheaply.

These basic materials should also, after being combined with an antioxidant ^{: g: omb; Lnat} (ia ⁾ i ^{L, result in} turbine lubricants with even better resistance to oxidation.

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The stated goals can be achieved by having a Uses a new class of synthetic esters as the basic material, those from a mixture of a dialkyl ester of isophthalic acid with a diester of aliphatic dicarboxylic acids and monovalent ones Polyvalent alcohols or a konocarboxylic acid ester Alcohols exist. It was also found to be extraordinary Good gas turbine lubricants can be formulated by adding an antioxidant combination into these basic materials incorporated from a phenothiazine or a substituted phenothiazine and a diarylamine, This combination can also be a sterically hindered phenol contain.

An essential component of the base material according to the present Invention is the ester of isophthalic acid. In the present description, under “esters of isophthalic acid” the alkyl diesters of isophthalic acid, i.e. m-phthalic acid, which correspond to the following formula:

In this formula, R- and Rp can be identical or different and represent primary or secondary alkyl groups having 4 to 2o carbon atoms. Preferably R and R contain 6 to 13 carbon atoms. The alkyl groups can be primary or secondary alcohols, they can also be straight

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chain or branched - the diesters can be pure or be of technical purity, i.e. up to about 15 liew .- '/ a i'erephthalate included.

The isophthalate esters preferred for one embodiment of the invention, aie for using basic mixtures with exceptional thermal stability and. Oxidation resistance and particularly favorable temperature behavior of the viscosity are those in which ti and ic each represent ilky groups with 3 to 10 carbon atoms, for example the n ~ uctyl, 2-ii.thy groups .lhexyl, n-iJon ^ l, isononyl, n-decyx, isooctyl and isodecyl. The preferred isophthalates include the compounds juizsooctyl isophthalate, di-2-ethylhexyl isophthalate, isooctyl isodecyl isophthalate, 2-iith, i.'lhex5-1-isodecyl isophthalate and diisodecyl isophthalate, of which di-2 ethylhexyl isophthalate is particularly preferred. -

The second essential component of the basic material according to the invention is a synthetic diester of an aliphatic dicarboxylic acid with monohydric alcohols or a ί ^ οηο-carboxylic acid ester with polyhydric alcohols. If aliphatic dicarboxylic acids are used to produce this synthetic ester, the monovalent radical usually contains 4 to 20 and preferably 6 to 13 carbon atoms. U-emic ones can also be used. Works aian with a y. Ethyl alcohol in the preparation of the synthetic ester, the ionocarboxylic acid has 2 to 20 and preferably 2 to 12 carbon atoms.

In the present invention, any of the foregoing can be used synthetic esters can be used together with the isophthalate esters. The following discussion is limited only for the sake of simplicity on the aliphatic dicarbon

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acid ester. These can also be interlinked be used. The ester group can be primary or secondary, ■> must be cig and branched, -preferred aliphatic dicarboxylic acid esters are the diesters of adipic acid and sebacic acid with alcohols with 6 to 10 carbon atoms.

as with the Isophth? 'latesters, are also suitable with the aliphatic These, some especially for the purposes of the present invention, are obtained, for example, with the .uiestern of adipic acid with branched-chain alcohols with 3 to 10 carbon atoms after deleting with the above especially resistant isophthalates (xbasic mixtures, The particularly preferred adipic acid esters include the compounds di-2-ethylhexyl adipate, diisooctyl adipate, Isooct ^ l-isodecyl-adipat, 2-ij.th ^ lhexyl-isodec ^ l-adipate and Diisodecjl-adipat.

isophthalate and aliphatic diester are commonly used in such u-evvichtverhäitnis mixed with each other, that about Dis about 2o G-ew .- ^ of the basic mixture of isophthalate, the reads is made up of aliphatic diesters. However, the preferred range for most gas turbine oils is at about 60 to about 86 weight percent isophthalate and 40 to about 14 weight percent aliphatic ester. The expert recognizes however easy, that is for the respective application cheapest special weight ratio of the used Isophthalate and depends on the aliphatic diester, the other additives and the exact purpose.

oind the alcoholic iteste in isophthalate and in aliphatic If there are different diesters, the esters can be synthesized separately and then mixed. Have isophthalate and aliphatic diester reads the same alcoholic, so the two esters can also be synthesized together

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will. For example, if one strives to produce a basic mixture of jji-2-ethylhexyl isophthalate and di-isodecyl adipate, the two esters are synthesized individually and then mixed; A basic mixture of 1) 1-2- ethylhexyl-isophthalate and 2-ethylhexyl-adipate, on the other hand, can be synthesized in one step by adding isophthalic acid and adipic acid to a sufficient χ, -. close 2-ethylhexanol. Complex mixtures, which are formed by reacting an alcohol mixture with isophthalic acid and dicarboxylic acids in one step, are also suitable for the purpose of the present invention.

The existing round mixtures are made resistant to oxidation at high temperatures by adding an effective amount of a known intioxidant such as ihenothiazine, jihenothiazine derivatives, secondary diarylamines or sterically hindered phenols to them. The antioxidants mentioned are only intended to serve as an illustration, but the invention is not limited to their specific use. Lie iintioxidants can be added to the basic mixture in amounts between about 0.1 and about 10 percent by weight, based on the u-esaiite mixture. i ^l or most Anv / extension events preferably r ^ to Lengenbach from about o, 5 up to about 5 wt .-><>, based on the o-esaiij-tgeinisch.

The present invention relates particularly to flowable ones jj'funktionstnassen, from the above-described ü-rundgeinischen and Certain antioxidants are made that prove to be special Effective for. ^ Stabilization against oxidative degradation at high levels I have proven temperatures. In this embodiment of the invention it is a functional, flowable mixture of (1) a basic mixture of an alkyl diester of isophthalic acid and a synthetic diester of aliphatic dicarboxylic acids with monohydric alcohols or of conocarboxylic acid esters

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Εit polyvalent. Alcohols, and (2) a binary antioxidant made from (a) Phe not hi a 2 in or a 1-henothiazine derivative and (b) a secondary diar.ylainin. In the present description, the term “phenothiazine derivatives” is understood to mean the IT-alkylphenothiazines and the mono- and ctialkyl-substituted derivatives of phenothiazines and the K-alkylphenothiazines, the alkyl groups of which have 1 to 20 carbon atoms. As examples of this ± ^; Henothiazine derivatives include iJ-A.th.yl-phenothiazine, dioctyl-phenothiazine and ri-i-iithyl-dioctyl-phenothiazine. The term "diaryiamine" includes the compounds diphen; ylamine, the l'hen ^ l-naphthylaiiiine and. the jkono- and .dialkylderivate of diphenylamine and the phenylnaphth ^ laniinen, whose alkyl groups have 1 to 20 carbon atoms. Examples of these dialamines are di-phenylamine, p, p'-dioctyl-diphenylamine, phenyl-Λ-naphthylamine, phenyl-is-naphth, ylamine, p-tert.-Oc t ^! Phenyl-.} ¹ -naphthylamine and p-tert-uct-1-phenyl-ß-naphthylamine. A binary antioxidant which is particularly preferred for the purposes of the present invention consists of the combination of N-ethyl-dioctyl-phenothiazine and ρ, ρ'-dioctyldiphenylamine. Usually the binary antioxidants individually make up about 0.5 to about 5 percent by weight, and preferably about 0.5 to about 2 percent by weight of the final formulation.

JiJs was also found to be the cost of the described J? ormulations can be reduced while at the same time the oxidation resistance is maintained or improved by adding a part of the relatively expensive phenothiazine derivative replaced by a cheaper, sterically hindered phenol such as a Laethylene-bisCdi-t-alkylphenol). The phenol can used in lengths between about 0.05 and about 5 G-ew.-yi v / erden, jjin particularly preferred ternary antioxidant consists

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_ A -

Km »

(a) o, 5-2 ΰ-ew .- ^ ä-iithyl-dioetyl-phenothiazine,

(b) o, 5-2 Grew.-f'o pjp'-Dioctyl-dipfaenylamiri and

(c) o, 1 to 2 ü-ew .-; - ö 4, 4 ^f - £ iethylene-bis (2,6-ai-t-but, y! phenol).

Any of the known viscosity index improvers can be added to the G-round mixtures according to the invention, e.g. Polymers and copolymers of acrylic acid and i ·. ethacric acid esters with C -, - to Cp -alcohols, with little or no phase separation being observed. These ^ -iCryiate and keu haCr ₃ latex usually have molecular weights between about 4,000 and about 2o,000. Typical of these .acrylates and iiethacrelates are the products that are sold, for example, under the trade name "Acryloid" by J ¹ InHa üohm <fe Hass. Other viscosity index improvers suitable for use with the basic mixture according to the invention are, for example, the polyalkylene glycols, high molecular weight polyesters, high-EOi-ecular polyalicans and lipolymers made from olefin and the abovementioned oils and kethacrylates. These viscosity index improvers can be used in amounts of up to about 10% by weight of the final formulation, but preferably amounts below about 5% are used. The named i-polymers can be synthesized according to the invention or in one-eat other suitable i made .ediuru and incorporated rundgeinisch above-in which then ßiit or without carrier.! 'the erfindungsgeniäiJen dcliiuiermittel can weitertiin any known .additive to improve ÜchExerfähigkeit and behavior contain extreme pressure as organic phosphites Particularly suitable additives for extreme pressure are the alkyl or hydrogen phosphonites and the jucine salts of the dialkyl phosphoric acid esters. ± ^v dr cTie most irasturbinenschriiiii.ttel preferred, this thrilling ability; .3additi ve and

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e ΓXv extr ^ uen! »jerk ν.ground usually in *. cti _b en from ofcv / ao, o1 to about i? ixow .-, J, based on the whole .ichniier- :: ittcl-xorüivlierung, used, lubricants that contain the erxin-.UD ^ egerr.tnJe w-rundgerfiiseh, can also known n una Let & j.lcieaictivators such as üenzotriazoi,

; ..,!, '- uisalie./liäen-alk.ylaiariiine and oebacic acid contain, particularly preferred are senzotriazole and sebacic acid, - ^ ieae ^ iüditive ainu ^ ewönnlich in x.iengen of about o, o5 to etv.-a 1, o uew .-; -, related to "the uesamtgeraisch available.

It is also possible to incorporate table aids into chillers which are based on the green mixture according to the invention. x ^; / i> ic additives of this type are dilicon antifoams such as the Ethylsilicone and -siloxane, oie are usually in quantities from 0.0001 to about o, oo2 G-ew. -ρ, based on the overall formulation, added.

In the following examples, x'eile always denote gray-weight parts, based on the total mixture, if nothing else specified v. is.

hin u -round ^ tifliisch. v for a gas turbine lubricant / ill be prepared by reacting 77.79 i'eile mixed di- (2-eth _t> lhexyl) isophthalate ruit 17.17 x'eilen iji- (2-äthylhe ^ l) adipate, iiann v.ird the following ILOKbination of additive dieaem added:

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- 1ο -

) j jilkyl-polymethylDiethacr ^ lat in neutral oil

Hi ¹ 348 ", Manuf. Ftohm &. Haas) 1,5o i'eile

E- ^ ethyl-dioctyl-phenothiazine ■ 1.5o "

ρ, ρ ¹ -dioctyl-diphenylaniin 1.5o "

i'rlcresj?! phosphate o, 5o "

iienzotriazole - o, oo2 '·

debacic acid 'o, o25 "

, Example 2

A basic mixture is made from 71, o files I> i (2-ethylhexyl) -isoph.th.alat and 24.445 parts of diisodecyl adipate, The same ^ dditive ^ combination is used in this basic genius as in example 1 added with the difference that rean only 1 part of the Soy-I-Olympic methyl methacrylate-Ueutralöl-G-emischs clogs.

Example 3

Turbine lubricant is made up of the following components formulated:

i) i (2-ethylhexyl) isophthalate 78.52 parts

M (2-ethylhexyl) adipate 17.28 "

y the trade name 7o7 ", manufacturer iiohm & Haas 1.5o"

"1, oo"

ϊί- ^ thyl-dioctyl-phenothiazine o.85 "

4,4'-i "ethylene-bis (2,6-di-t-butylphenol) o.5o"

ϊ ric re sj lpho spha t ο, 5 ο "

Benzotriazole o, o2 "

b'ebacic acid o, o25 "

(Antifoam agent) 5, ο ppm

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The ochr, iermittel of! Examples 1, 2 and 3 are according to the x'est method of j> 'ord iotor Oo. for turbine lubricating oils (^ o (J-ii2C125-ü) tested, the results are in the following Table I summarized:

table I.

Conditions for the test method lubricant according to example

"" "A 1 2 3

3.2 Viscosity (cSt)

3.2.1 at 163 ^ 0

(AuX ¹ M 341) 2, ο cdt (min) 2, ο 2, ο 2, ο

3.2.2 at 99 ° C 5, ο eist (min) 5, o2 5, ο 5.16 (AOi ¹ L D445) 7, ο cat (max)

3.2.3 at 37.3 ° above sea level

(ΑϋΐΜ 1) 445) 2o (min) 31.14 31.5 32.15

3.2.4 at -17.3 ° 0

(Aoi ^r M D26o2) 2ooo cP (m _a x) 1776 1913 I3o2

3 »3 ^ top point

CAJi ¹ E = Ό97) -6.7 o (max) -62.2 ° o -59 o -45.6 ° u

3.4 i ^? lash point 218 ° O (min) 227 ° <J 229 ° ö 224 ° ^

3.5 ^ ntzlinduiifisteiap. 232 ° C (min)
TUW ~)

3.6 Health acid number 0.5 mgKOIVg 0.23 , 25.0, 29

CAoiL i) 664) (max)

3.7 Loss of evaporation
ücii'k D972;

C 9;

Vj at 149 O ₁ 22 ötd. 2, ο (max) 1, o 1.0 L ', o7

.ibs.1 (jibsetzzeit) 25 lül (υ) <fio (υ) <^ 10 (ü) <riu (ü)

^ ibs.2 (Abeetzzeit) 25 sal (ü) <10 (ü) <T1ü (υ) <1Ü (υ)

Paragraph 3 (^ bsetzzeiw) 25 ul (υ) <10 (ο) <1O (θ) <10 (θ)

(79,

method 5321.1) 1 ^ /

CHi "112 (min) 158 172 179

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■ abelle I (üVorts.)

conditions

'Ie stiiiet ho de lubricant. .Be is ρ, 1 -2 3

5.1ο JuD Üle! Korrosion (J) ¹ J ¹ I ¹ It 791 ji, Lethbde,

5321.1) mg / 6.45 cm ^

at 163 G, 1 hour 3, ο (mgx)

3.11 Corrosion and oxidation regulations

!, method 5308.6)

a. 175 G (72 ctd, 5, oil air / hr) viscosity change at -37.8 ⁰ G (γό) changing the Ge samtsäurezahl modifiers ^ .d.Metallgew, mg / CDi ^ - ü'ei (cJtah.l) Ag

Lg

Gu

Deposition (sludge) after 1 ο / U-j? Il entered ion no bed.

J3.2o4 ° 0 (72h., 5, ο

air / hour)

Viscosity change t) ei 37.3 ⁰ G ($)

Ver rand. d. Total acid number

Change in metal weight

mg / cm i'e (steel)

■ Ag
al

Gu

so so.

3.0. SO. SO. SO. P .0.

no

+0.16

-5 'to +15 8.93 8.0 3.92 2, o o, 99 o, 74 o, 75 + o, 2 +0, o1 0.0 0.0 + o, 2 -0.07 -0.46 -o, o51 + o, 2 0, 0 0.0 0, 0 + o, 2 0.0 0.0 Q, O + 0.4 0.0 -0, oo3 -o, o27

none none

12 _; 2 13.5 7.6o 436 5.98 7.39 0.03 0.0 + o, o19 -0.03 0, 0 -o, oS6 +0.01 0, 0 0, 0 0, 0 -0.12 -o, o27 -o, 27 -o, 27 -0.137 no no no permissible admissible permissible

Deposits (sludge) after 1o / u filtration see above

3.12 Sediment allowed

3.13 coking open -

3.14 Compatibility with commercial Lubricants 3.14. \ l_ 1: 9, 1: 1 with

recognized oils heated to 149 ⁰ O (2o hours),

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2312G22

ϊεbelle I (always.)

Conditions

! Test method lubricant according to example iiiJw-lii; 2ül125-A 1 2 3

cooled to -Z9 ° g / no sediment allowed

o, oo5 ml / 2oo with ml of Stauffer

Jet II

3 14 2 iJlastomer

Trä _e friendliness with the

Compound 934 ^ 32

the National üeal Oiv.

at 2o4 ° C (72 hours)

; o ^ uellung 1o + 5 1o, p

admissible allowed with with Stauffer Stauffer Jet II Jet II

11.7

11.44

extrapolated.

It can be clearly seen from Table I that the lubricants of the Examples 1, 2 and 3 meet the requirements of the i'ord-'iest method have grown.

Scnmiermittel of Examples 1, 2 and 3 were further after the 'i ¹ estverfahren of "Naval Air Systems Command, Department of the Nav ^ -Vorsclirift XAS 2354, para. 3.4.4" tested, which were obtained from Table II apparent Results ;

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- H-

Table II 'χ ¹ est conditions: 149 ⁰ G hours 2 3 i 'temperature i. oil 288 ⁰ C O 357 32V the temperature d. lower tube 1,000 cm / min. Examples 12, ο 5, o Air volume 48 1 6.8 8, o i'est duration 93 ° 357 O 31, ο temperature d. Chamber . 18.0 97 5o i'est results: 9.3 o, 9 31.68 32, o crit. i ¹ empe ra door, ° G 71 34.8o 35, ο Assessment of the deposits 36.12 33.4 liohral deposition, mg 31.31 +4.44 +6.4 jj 'filter deposit, mg 36.35 14th 2o, o Oil consumption, ml 4o, 5o Viscosity at 37, S ⁰ O (cSt) +9.19 o, 24 o, 28 Beginning 29 2.18 1.92 24 hours 4 t ^oo 3, o9 48 hours o, 23 +3.76 +2.31 change 2.2o > j increase 4.1 ο Total acid number (mg KOH / gm) +3.87 Beginning 24 hours 48 hours change

(Depending on the valuation

14.1

9.4

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Example 4

uin G-rundgemiseh is made from 70 'files i'riuiethylolpropane-triheptanoat and 30 x'eile x) i- (2-ethylhexyl) - isophthalate, this ixrundgeinisch. 1.5% of a viscosity index improver are added in the form of the rolymethacrylate "Acryloid HJb ^l 343" ♦ The resulting formulation shows the following properties:

Viscosity (cot)

99 ° above sea level 5, o3

37.3 ° above 29.34

-17.8 ⁰ O 1339

Viscosity index 1o7

Example 5

. ^ in ürundgemisoh from 75, ο x'eilen i'rimethjlolpropanetrriheptanoat and 25, o x'eile i) i- (2-ethylhexyl) isophthalate manufactured. To do this, 1.25 x parts of the viscosity index improver are used mixed in according to Example 4. The resulting formulation has the following properties:

Viscosity (cat)

99 ° 0 5, o5

37.3 ° 0 3o, 18

-17, 3 ° υ 1459

Viscosity index. 1o3

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Example 6

^{1 part} xi-imethylolpropane-triheptan.oat are mixed with 2o Cfewichtsteile jji (2-ethylhexyl) isophthalate and 1, o ¹ part polymethacrylate like 3 Example 4 mixed. The resulting formulation has the following properties:

Viscosity (cot)

99 ° O 4.95.

37.3 ⁰ CJ> o.95

-17.8 ° C 1653

Viscosity Index - 3'j

.. earth the jj'orssiulierunden of the ^ eiopieie 4, 5 and G ljxI; · Χ üx ^ ends Mixed with additives, you get a-eciocue, that of the Introductory mentioned i'orä-i'esü prefix entapachen:

N-i-thj / l-dioct.yl-Tjhenothiazin 1,5o x'eile

ρ, ρ'-xjioct ^ l-diphenvlaDiin 1,5o "

x'ricresyl phosphate '0.5o "

Senzotriazole o, o2 ""

Sebacic acid o, o25 "

Example 7

round material consisting only of isodecyl adipate mixed with the YidditivkoE-combination according to example 1. Jie The resulting alignment is then included in the oxidation test 2o4 ^ (see Table I) subject. That’s going to happen results obtained in table III:

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SAD ORIGINAL

xable III

Verse.

Vera.

Change in virility at 37.3 Change in total u-total acid number Change in ketail weight

/ cm

ei ta hl

deposit

1o u-jj'iltration

after

; 3.3% 16.1o

-0.992

+ o, o15

no

-0.069

-1.223

24, o? Ö

2.1% 16.10

-1, o39 + o, o23 none -o, 77 -1,231

23, 0 ^

It can be seen in Table III that refining agents on the basis of ^ d ^ ijpine acid esters such as the oriuuliemng of Example 7 are favorable with regard to the change in viscosity. However, they are never too dirty, that is, the formation of sediments is too strong, furthermore they are too strongly corrosive to calcium and copper, so that they are unsuitable for use in gas turbines, as is the formation of acids in such

opposes such use.

.-, in consisting only of i'rimethylolpropane triheptanoate Base material is diluted with the additive according to ± 3 example 1 the ^ 'orientation is used in the ex ^ dation test

2o4 ° U genial x'abeile I subjected. Thereby the following

results achieved:

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- 13 -

Sabelle IV Verse'. 1 Vers. 2 74.3 75.6 Viscosity change at 37 »3 ° λ>
(c3t) 10.72 11.38 ■ Change total acid number ο, οβ o, o4 Change in metal weight, mg / cm
Lg ο, οβ ο, οβ dt a hl -ο, Η -0.18 λΙ -ο, 78 -o, 32 Ag

Deposits (ochlamm) after

1o u-x ' ^l filtration, ' - /> 4, ο 5, ο

Examples 9-14

These examples show the surprising benefits that come with Use of certain binary antioxidant combinations in connection with the basic principles according to the invention result. - Examples 9 and 1o represent a lie formulation of the lubricant according to Example 1. Examples 11 and 12 agree with Examples 9 and 1o with the difference that 1.5 parts of p-t-octylphenyl - ^ -najahthylamine used instead of ρ, ρ'-dioctyl-diphenylamine, furthermore Examples 13 and 14 agree with Examples 9 and 1o with the difference that 2.35 parts ρ, ρ'-iüioctyldiphenylamine are used and no IST-Ethyl-dioctylphenothiazine is available. The "formulations are then subjected to the oxidation test at 2o4 ° ^ according to Table I, with the following results:

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i'abelle V

.Examples 9 1o 11 12 13 14

Viscosity change

at 37.8 ° υ (> 0) 3.6 1o, 3 23.9 13.4 27.4 19.2

Yeränd.d. total acid number 5.91 6, o3 7.7ο 6.46 2ο, 34 17.34

Change of ketallgew.

IKg / CHI ²

kg + opo3 + op23 + ojo23 + op31 + o, o39 + op39

Steel + o / D23 + op15 none none + opo3 + op15

Ag -op69 -ορ92 no -ο, οοΤ -op69 -op54

Al + opo8 none none none none none

üu -ο ^ 77 -o ^ 15 -op92 -op23 -oß39 -0.654

deposit (ochlamm)

after 1o / U filtration none none 2, ο 1.5 3, ο 9, ο

Investigation of the ürg-ebnispe of x'abelle ¥ shows that the formulations which contain a binary antioxidant combination of a phenothiazine and a secondary üiarylamine (Examples. 9, 10 and 11 and 12) are similar formulations which contain only a single -antio- ^ have dating agents, both hxn: -3visible 'change in the acid number • are never noticeably superior in terms of sedimentation, it is particularly surprising since, as is well known, the ρ, ρ ¹ -dioctyl diphenium laminate is usually a much cleaner antioxidant (ie low sedimentation pi * oducing x,} dationic agent) is than other 6: ydantien, whereby the substituted phenothiazines are regarded as less clean, it can also be seen from table Y that the lioBibination of egg-thyl-dioctyl-phenothiasin and p, p '-Dioctyl diphenylamine is particularly beneficial due to the small change in viscosity that accompanies it.

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Example 15

A lubricating agent is based on the instructions in Examples 9 and 10, but no viscosity improvers are used. The resulting ^ -oriulation gives in the Ox, ydationstest at 2o4 ° ^ according to 'Table 1 in each category rcit the results of .Examples b ¹ and. 1o comparable, with the exception of the percentage. Visco si'cats change at 37.3 ° above sea level, at which the alignments according to the example result in the values of 22.2 and 2o.5 (in general the values of Examples 9 and 10 are 3.6 and 1o, 3) It is therefore often advisable to use a small amount of a viscosity index, -beaser of the rolyacr ^ lat or pol ^ iethacr ^ lat type, not only to improve the viscosity index, but also to improve the resistance to oxidation at high levels i'emperaturen.

-Example 16-

i!) in a mixture of 55,000 parts of diisodecyl isophtholate and 41.455 parts of isodecyl iidipate is produced the additive combination according to example 1 added, however, without l-olymeth.yl-meth.aer, ylate. I; the resulting lubricant has the following properties:

Table VI Viscosity (cJt) 99 ° ^ '. 5.27 37.8 ° 0 33.66 -17, S ° above sea level 1947 Viscosity index 95 evaporation o, 71> * Acidity 0.37

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However, the formulation behaves just like the

Example 15, not as good as the cancellation von ^ eisioiel 1 due to the missing viscosity inex / erbesserer.

3098A1 / 08Ü8

Claims (1)

Claims 1. Suitable for use in gas turbine lubricants Basic lubricant mixture containing (a) about 2o to about 9o Grew .- '; j of an isophthalic acid ester. the i'Ormel Il COIL in which R ₁ and K _{2 represent} primary or secondary alkyl groups with 4 to 2o carbon atoms and (b) about So to about 1o Ü-ew .- ^ of a synthetic diester of aliphatic dicarboxylic acids with monohydric alcohols or an ivionocarboxylic acid ester of polyhydric alcohols. 2. ü-emisch according to claim 1, characterized in that it about 6o to about 36 wt .-> of the ioophthalic acid ester and about Contains 4o to about 14 wt .- / o of the synthetic ester. 3 · G-egg according to claim 1, characterized in that it. uad .rtp are alkyl groups with 8 to 10 carbon atoms. 4. ü-emisch according to claim 1, characterized in that it as isophthalic acid ester di-2-ethyxhex ^ l-isophthalate, liisooetyl-isophthalate, Xsooctylisodecyl isophthalate, 2-ethylhexyl contains isodecyl isophthalate or uüsodec ^ l isophthalate. 309841/0808 2312B22 b. Mixture after. Claim 4, characterized in that it _üi-2-ä "ühylhex,) l - contains isoprithalate. 6. U-emic according to claim 1, characterized in that it is as synthetic master adipic acid or oebacic acid aiest of alcohols with 6 to 10 carbon atoms. 7. Mixture according to .Anspruch 6, characterized in that it as synthetic dark adipic acid diester with branched chain Contains alcohols with 8 to 10 carbon atoms. 3. Mixture according to claim 1, containing (a) about 6o to 86 & ew .- '/> an isophthalic acid dialkyl ester with alkyl groups with 8 to 10 carbon atoms and (b) about 40 to about 14 ew .-> ä of a dipinic acid ester with branched-chain alcohols with 8 to 10 carbon atoms. 9. G-emisch according to claim 3, characterized in that it as isophthalic acid ester jji-2-eth / lhexyl isophthalate, misooctyl isophthalate, Isooctyl isodecyl isophthalate, 2-ethylhexyl isodecyl isophthalate or contains iisodecyl isophthalate. 10. G-emic according to claim 3, characterized in that it Contains di-2-ri.thjlhexyi-isophialate and di-2-ether-1hexyl adipate. 11. U-emic according to claims, characterized in that it Contains jJi-2-ethylhexyl isophthalate and diisodec ^ l-adipate. 12. Gas turbine lubricant, characterized in that it (1) a lubricant base mixture according to claim 1 and (2) one to stabilize the lubricant against oxidative Degradation of sufficient amounts of an anti-oxidant combination from (a) I'henothiazine or a phenothiazine derivative and (b) a secondary dial laminate. 309841 / 0ÖU8 _ O ή _
- £ -4 - 13 · lubricant according to claim 12, characterized in that the isophthalic acid in a Ivienge corresponding to about 6o to about 86 wt .- $ of Cfrundgemischs and snythetische iister in an amount corresponding to about 40 to about 14 wt. F> of the G-round mixture is present. 14. Lubricant according to claim 13 ». characterized, that it contains the antioxidant combination in an amount of about 0.1 to about to wt .-? b, based on the total Lubricant formulation. 15. Lubricant according to claim 13, characterized in that the phenothiazine or phenothiazine derivative and the secondary Diarylamine each in a quantity of about 0.05 to about 5.o weight-70, based on the total lubricant formulation are present. 16. Lubricant according to claim 13 »characterized in that it is N-ethyl-dioctyl-phenothiazine and ρ, ρ'-dioctyl-diphenylamine each in an amount of about 0.05 to about 5 wt .- ^ ί, based on the total lubricant formulation. 17 · Lubricant according to claim 12, characterized in that it additionally contains a viscosity index improver. 18. Lubricant according to claim 17 »characterized in that that it contains a polymer or copolymer of an acrylic or methacrylic ester as a viscosity index improver Contains Gp to Op alcohols. 19. Lubricant according to claim 12, characterized in that it contains a basic mixture (1) according to claim 8. 2o. Lubricant according to claim 19, characterized in that 3098Λ 1/080 a it as a phenottiiazine derivative tf-ethyl-dioctylphenothiazine contains. .ν- 21. lubricant geroäi3 Claim 19 "characterized in Daii ρ it as a secondary diarylamine, contains ρ'-dioctyl-diphenylamine. 22. Sehmiermittel according to claim 19 »characterized in that as isophthalic diester di-2-ethylhexyl isophthalate, isooctyl isophthalate, 2-ethylhexyl isodecyl phthalate, isooctyl isodecyl isophthalate or diisodecyl isophthalate contains. 23. Lubricant according to claim 19j, characterized in that that there is also a polymer or copolymer of an acrylic or kethacrylic acid ester as a viscosity index improver with Gp to Up alcohols. 24. Lubricant according to claim 19> characterized in that If it is a basic mixture (1) according to claim 1o and an antioxidant combination (2) from (a) !! - Ethyl-dioctylphenothiazine and (b) ρ, ρ'-dioctyl-diphenylamine. 25. Lubricant according to claim. 24, d & marked by, that there is also a polymer or copolymer of an acrylic acid or I ethacrylic acid esters with G "- to 0 -alcohols as vis ^ Contains cohesion index improvers. 26. Jchmiermittel according to claim 24 »characterized in that that IT-ethyl-dioctyl-phenothiazine and p, p'-dioct ^ l-diphenylamine each in a range of about 0.05 to about 5 G-ew.-ya, based on the total lubricant. 27 · «Dieting agent according to claim 26, characterized in that daw it is in addition to about 5 wt .- ^ i of a polymer or 30984 1 / 08U8 • - 26 - Copolymers)! of an acrylic or luethacrylic acid ester with C "-bis Cp alcohols, about 0.1 to about 5 wt .- ^ i'ricresyl phosphate, about 0.05 to about 1.0 percent by weight of both benzotriazole as in sebacic acid and about ο, οοοΐ to about 0.02% by weight of a dilicon antifoam agent, the percentages being based on the weight of the total lubricant. 28. Lubricant according to claim 26, characterized in that there is additionally about 0.05 to about 5 wt .-? I of one through contains a methylene group linked, sterically hindered bisphenol. -. D _a ii in 29 · lubricant according to claim 28, characterized in that the bisphenol is ^4,4'-Iv: contains ethylene-bis (2,6-di-t-butylphenol). 3o. Lubricant according to claim 19, characterized in that it contains the basic mixture (i) according to claim 11 and as an antioxidant combination (2) a mixture of (a) U-ixthyldioctyl-phenothiazine and (b) contains p, p'-dioctyl-diphenylamine. - 31 · Lubricant according to claim 3o, characterized in that it additionally contains a polymer or copolymer of an acrylic acid or methacrylic acid ester with GP to Op alcohols as a viscosity index improver. 32. Lubricant according to claim 3o, characterized in that it-iithyl-dioctyl-phenothiazine and p, p'-dioct, yl-diphen, / ia; i] in! .Engen from about 0.05 to about 5 ' iew .-) j, based on the entire lubricant. 309841 / 0SU8 33 · Lubricant according to claim 32, characterized in that it additionally bia to about 5 wt .- ^ of a polymer or copolymer of an acrylic or kethacr ^ 'l acid ester with C ^ - to C ₂ alcohols, about 0.1 to about 5 ixew .-> i l'ricresyl phosphate, about 0.05 to about 1.0 wt .- ^ both of benzotriazole v / ie of sebacic acid, and etv / a ο, οοοΐ to about 0.02. -fö of a silicone - Contains anti-foaming agent. 34. Lubricant according to claim 32, characterized in that it also o, o5 to 5 wt .- '/ ό based on the total lubricant, a sterically hindered biphenol bridged by a methylene group. 35. Lubricant according to claim 34 »characterized in that it contains the .Bisphenol 4,4 ^f -Liethylen-bis (2,6-di-t-butylphenol). Stauffer Chemical Company
v.estport, Conn., V.St.A «. Dr. H. J. Wolff Lawyer 309841 / .0 808