DE2240298A1 - LUBRICANT MIXTURE - Google Patents

Description

in the. IA ti. ί- :. π ·.) ΐη> ΊΐΑΝΝ ■ dipl. ίκα. w. vain · dr. he «, ν at. κ. ηογρκανν

PAT «N T AN WA Ι / Γ K D-SOOO MC HEN Sl · AItABEUASTRASSE 4 · TELEPHONE (Olli) »Γι« Ϊ7

Mobil Oil Corporation, New York, N.Y. / UNITED STATES

“V

Lubricant mixture

The invention relates to lubricant mixtures improved stability properties. ' The invention relates in particular to lubricants with a low Amount of an additive have been added which is capable of reducing oxidative decomposition of the lubricant.

It is known that lubricants tend to oxidize if they are detrimental during storage or use Conditions are exposed. This can take place, for example, in the lubrication of combustion engines, where the Oxidation at the high temperatures present and in the presence the construction part is greatly accelerated.

The oxidation of the lubricant can lead to a loss of the lubricating properties. If this loss is enough is strong and enough remains undiscovered, then the The engine will become completely inoperative. However, this decay can be detected because it is generally of a Increase in acidity or viscosity or both properties is accompanied. This can be determined using conventional tests.

Although a test for a breakdown of the lubricant .and maintaining effective lubrication

309819/1165

BAP ORIGINAL

are generally acceptable through periodic renewal or replacement of the lubricant, the, το However, measures come very expensive. So there has been a search for additives which prevent or prevent oxidation at least greatly reduce. A pint of the well-known additives, used on a large scale as antioxidants for lubricants used v / earth, is the class of Asainö ^ in particular the Diarylainine.

Another class of known antioxidants is the class of the t-alkyl substituted diarylamines. In the US patent 3 A14 618 describes that tertiaralkyl-substituted Diphenyl-, dinaphthyl- or M-phenylnaphthyls.Kin as Antioxidant used for a synthetic lubricant can be.

The use of the etherified Diarylainine as antioxidants for lubricants is however has not yet been prescribed.

The present invention relates to a lubricant mixture which comprises a main amount of a lubricant and a an amount of a compound of the general formula sufficient to improve the oxidation properties

contains, in which Ar and Ar 'are phenyl, Iaphthyl, phenanthryl and / or anthryl, R and R ¹ / ilRyl ^ ruppen mix 1 to 20 carbon atoms are badaiten and m and η 0 to ' j , at least one of these numbers being at least 1 is.

The invention also provides a process for the preparation of the above-mentioned compounds, which is characterized in that is L that Kau is a hydroxy derivative of the above

3 0 9 8 19/1155 _BAD

Compound (ie, one in which R _f, or R ¹ is hydrogen) halide in a Dialkylformaraid as solvent or in dimethyl sulfoxide or acetonitrile in the presence of an alkali metal carbonate, is reacted with an alky!.

This manufacturing process is considered new. The known Methods of making the compounds include the preparation of the alkali metal derivative of the starting hydroxyl diarylamines before reacting with an alkyl halide. These Measure is "necessary in the known methods because in the absence of the alkali metal derivative in considerable Measure a competitive reaction of the alkali halide with the amine function takes place. If, as provided herein, the reaction in the presence of an alkali inotallcarbonats and a suitable solvents,., then there is no d.ie Necessity to prepare the alkali metal salt of the aminophenol in a separate first step.

The reaction of aminophenol with alkali metal carbonate (in which the term "alkali metal" wa tr ium, lithium, potassium and Caefjiiici, intended to include) is not just an in situ reaction. It seems that the iJimethylsulfoxyd, acetonitrile or the Dialkylformamide, but especially dimethylformamide, a exerts a selective effect in order to produce an etherification by in the examples given below, a yield of the etherified product of up to 97 / £ is obtained. on the other hand the same reaction, when carried out in different solvents, produces a significant amount of the I \ [- alkylation instead of etherification.

Bej .. illustrates implementation of UiniF.-etsung according to the present invention may range from about 80 am about 200 ⁰ C, preferably expected from about 130 to about 150 ⁰ C, good product yields. The reaction can usually be completed in 2 to 3 hours, but it can also be several hours

11 pp

BAD0BK31HÄL

22A0298

Hours, e.g. up to 10 or 12 hours, depending on the temperature and the specific Respondents depends.

Generally speaking, it can be said that the aminophenol and the alkyl halide, especially at low temperatures, can be used up to a Ho! ratio of about * 1.5: 1 can. However, this ratio should 'preferably be around Be 1: 1. When carrying out the procedure, each equivalent dos Aw.irjophenols about 1 to about 10 equivalents, preferably Vierden used about 3 equivalents of the carbonate.

The lubricants that have been improved by the alkoxydiarylamines are mineral and synthetic lubricating oils and greases made from them. The mineral oils should not only include paraffinic oils, but also the nephthenic products. Synthetic oils are to be understood as meaning synthetic carbons, polyalkylene glycols, polyacetals, polysilicones and the like, as well as synthetic ester oils. Of products of the latter type, there may be mentioned, for example, the esters obtained from monohydric alcohols and polycarboxylic acids, e.g. In particular, the products of the latter group are important. These include esters made from the trimethylols, e.g. their ethane, propane and butane derivatives, 2,2-disubotitu-sertone propanediols and pentaerythritol with aliphatic monocarboxylic acids having from about 4 to about 20 carbon atoms. Geraische of these acids can also be used for the production of the esters. When carrying out the present invention, preference is given to the esters which are prepared from pentaerythritol and a mixture of C _r - to Cq acid. In the preparation of such esters, a generally acceptable product of technical

3 0 9 8 19/1155

BATH ORIGINAL

Shem pentaerythritol obtained from about 88? o of the Kono-Forra and contains about 12Jo of the Di form.

-The additives of the present invention can be used at a concentration from about 0.005 to about 10% by weight, preferably from about 0.1 to about. 5 weight fo, based on the lubricant, can be used. . ■ J

The invention is illustrated in the examples.

Example 1

4 ~ n ~ 0 ctoxydiph enylainin

A mixture of 19 g of 4-hydroxydip.heiiylamine, 16 g of 1-chlorooctane and 57.6 g of anhydrous potassium carbonate in 150 ml of N, N-dimethylformamide was refluxed for 6.5 hours. The resulting reaction mixture was cooled below 100 ° C. and poured into a large excess of cold water. The resulting crystalline solids were collected by filtration. In this manner, the 4-n-0ctoxydiphenylamins obtained with a melting point of 42-43 ⁰ C 29.5 g (97/0. '

Example 2
2-methoxydiphenylamine

A mixture of 50 g of 2-chlorobenzoic acid, 66.1 g of anhydrous potassium carbonate, 79 g of 2-methoxyaniline and 300 ral of diethylene glycol dimethyl ether was heated to 140.degree. To the mixture, about 1 g of copper bronze and about 0.1 g of copper iodide was added and it was heated to 140 to 145 ° C while the stirring was continued for about 3 hours. "The reaction mixture was cooled to about 100 ⁰ C and poured into water ./The v / aqeous mixture was filtered and the filtrate was acidified with acetic acid, heated to boiling and filtered

309819/1155

these V / else vmrden 58 g (75 ^r, a) of tan, crystalline substance 2-methoxy-diphenylamine-2'-carboxylic acid, mp 171-172 ° C, was obtained..

Heated £ 171 ^2-I-2-l -carboxylic acid lethoxydiphenylamin vmrden 5 hours in einor nitrogen atmosphere at 260 ⁰ C. 2-Metho.xydiphenylamin was distilled from the resulting reaction mixture as a pale yellow oil, bp. At about 6 19Ö ram Hg to 204 ⁰ C.

Example 3

4,4'-dioxydiphenylamine

Portions of 5-0 g of sodium metal chips were added to a solution of 50.3 g of 4,4'-dihydroxydiphenylamine in 250 ml of diethylene glycol diraethyl ether. The addition was started at 8O ⁰ C. It was necessary external cooling to maintain the temperature at a Ilaximum of 10O ⁰ C. After all of the sodium had been consumed (approx. 0.5 hours), 96.6 g of 1-brorooctane were added at 100 ° C. over a period of 1.5 hours. Heating and stirring were continued for 4.5 hours. The reaction mixture was filtered off and poured into water. The crude 4,4'-dioctoxydiphenylamine (90 g) that precipitated was collected by filtration. The pure dioctoxydiphenylamine was obtained in the form of silver-colored, soft flakes with a melting point of 76 to 77.degree. C. by recrystallization from ethanol.

Example 4

3-octoxy-4-tert-octyldiphenylamine

Bin mixture Aya 75 g of 3-Octoxydipheaylaain and 39 "2 g of diisobutylene was heated to give a homogeneous solution. 1 g of anhydrous aluminum chloride was added to the homogeneous solution and the whole was heated to 135 ° C. for 6 1/2 hours. To

309819/1111.

S ORIGINAL

... 22-0298

During this heating period the olefin became unreacted removed by distillation and the residue was dissolved in ethyl ether with a dilute aqueous potassium hydroxide solution and. finally washed with water. After drying, the solvent was removed by distillation. The residue gave the product which had a boiling point of γ235 to 240 ° C at a pressure of less than 0.1 mm Hg.

The following additional ■ products were manufactured using the specified methods:

example Designation made n 4-Athoxy DPA ¹ ■ "' /"Experienced dom ^ 3-octoxy DPA pie D. s Be.iG] 4-octoxy DPA 2 5 4-0cto: sy PAN ² 1 6th 4-uecoxy PAN 1 7th 3-dodecoxy DPA ■ 1 8th 4-dodecoxy DPA 1 9 4-octoxy I ⁵ BN 1 10 4-decoxy PBN 1 11 4-octadecoxy PBN 1 12th 3-benzyloxy DPA 1 13th 4-benzyloxy DPA 3 14th 3-dodecenyloxy DPA 1 15th 4-dodecenyloxy DPA 1 16 4- (2-ethylhexoxy) DPA 1 17th 3-isopentoxy DPA 1 18th 4-isopentoxy DPA ■ 1 19th 4-octoxy-4-tert-octyl DPA ' 1 20th 4,4'-diisopentoxy DPA .1 21 N-phenyl-1 - (2-metho2ty) -naphthylamine, 4th 22nd N-phenyl-1- (4-octoxy) naphthylamine, 3 23 2 24 2 ......- ■

309819 / 11S6

26 _t NP]) f ^j r'yl-1- (Cc) cto: -; y) -n:; j.) Lrthylaniin ί

? -7 4-methoxy PAN 1

28 / i-ethoxy P / JJ 1

'"Phony! - 1 ~ naphuylamine

Phenyl- ^ .- naph thy lai / iin

l) ic ηΓ.ΐ'Λ ^ Χ'.ΐ'ί ./. ί.'ί /, - οΜ'Ιί; JKTgeytollteii Ycrbiwiun ^ oii v / urdun in ci;: j

von Poirr. ;; O.vythrit J ^ i ¹ I. an aqnjj'iolarcn Gejaiüc;) i from C, (! ₍₎ ~ i ^v lo) iooarboxii-jauren) eii ^ emiscjit ιιηύ j-io.ch the- following 1-iOtiiode u.ir!: EriJiJ.cbt ·,

liiiiO Pi-obc de.'i Tci. '. [: r; ci-iiscjitü was ej ^ heats. Lu: Ct of 2;> ^ ° C (/; | jO ³ P) v / ui'uo üi; er cii'jc-n /'e.it.i'r;.um vosi 2 '; Hours with cinc-r Gor.chvir'dJü'.o.rL vo? .I 5 'l / h through ^ eicit (; 1 ;, In ücr test sample were specimens on ::; Eiaen, Kup.for, aluminum and lead enl; ·· haiton. the ti ο metals üi.nd. typir, .che rictalle füi ¹ Ilaschiiicra-): cni5trul; tio3 ^ on. w'citcrlij.n go d.iof; o Mctallo Katalj ^ «a" Lorovj for the oxidation of oTY ;; an.i.üchcii I-üatorialien. The original buildings are 5.n of the Xolcenden! i'abellc Z (if: ; aminenr; e ^ tellt. The "change in the kinematic? ·) Vinkoeitat, [^ anessen in Ceiitiütokez :; at y / _f B ° C (-1CO ⁰ F) (% KV change), and the change in the neutralization rate (liZ change) are measures for the Virkßixrfikei.t of / uit; if: - '\' dont. i en in . ''! eV-iiiierriiittf; !!!,

309819 / 11B5

BADORIGtNAL

■ - 9

Additive
Example - 3 Additive Temp.
o _{c (} 6 _F) Anfancjc-
IJZ A ITZ / rnfangn ---
KV ^ eDt
D. 37.8 ° C Λ KV, B chi αν ii'f!
LiI-
dun - ;;; O ... 219 (425) - 5.9 - 226 no; 232 (450) 8.3 - 585 Traces" 1 2 219 (425) 0 1.0 25.72 17th Spin-on 4th 1 1.0. ' 14th traces 2 232 (450) 0 η 6 - '? - 25.72 191 easy 1 7.6 180 traces 2 2 219 (425) 0 1.3 25.28 24 traces 5 1 3.6 51 Haunted 2 232 (450) 0 5.1 25.28 88 Trace}.! 1 5.6 95 loicJvb- 6th 2 219 (425) 0.25 0.87 . 28.67 19th no 1 - · ■ 0.93 11 no 2 232 (450) 0.25 7.97 28.65 ' 79 Spuron 1 2.43 111 traces 2 219 (425) 0.1 1.25 28.85 19th .Traces 1 1.47 13th traces 7th 2 232 (450) 0.1 2.95 28.96 Ti no 1 1.97 2 no 4th 232 (450) 0.3 3.6 26.32 90 strong 2 3.6 61 star!: 1 5.9 97 strong 4 · 219 (425) 0.03 1.25 27.25 46 no 2 1.27 30th easy 1 1.08 29 . easy 4th 232 (450) 0.05 1.85 27.25 64 no 2 1.57 45 no 1 2.68 59 no 4th 219 (425) 0.05 1.25 26.84 59 - traces 2 1.07 32 no 1 1.53 22nd no 4th 232 (450) 0.05 2.65 26.84 110 ke.i no 2 1.87 69 no 1 2.38 66 no

3098 19/1155

© AÖ

Additive Gev / .ji Te * Example additive ⁰ C

12 13

14th

8 4 2

9 2

1 2T9 4th 2 1 232 4th 2 1 219 4th 2 1 232 4th 2 1 219 4th 2 1 232 4th 2 1 219 4th 2 1 219 2 232 2

nitmiy; - Δ UV. Atlfi AT _{1 year}
KV ₁ CSt
b.37, Ü ° C Room KV,
% mud
bil
manure 0.05 2.65 28.63 63 no 1.07 98 easy 1, 88, 39 star]; 0, U5 1.25 _- [K .. 27.51 27 traces i, 05 40 traces 0.05 4.75 27.51 55 lioj.no 2.07 195 strong 0.05 1.05 27.47 46 easy 1.27 25th no 1, OfJ 84 strong 0.05 ■ 2.05 27.47 63, no "2.07 47 traces 3,4a 1CO traces 0.05 1.25 27.14 52 koine 1.27 27 no 0.78 28 traces 0.05 1.85 27; 14 86 no 1.57 64 no 2.38 77 traces 0.10 1.00 28.70 48 strong 1.05 63 strong 0.77 17th traces 0.10 1.20 28.70 48 strong 0.75 26th strong .1.07 29 strong 0.20 0.60 29.09 24 moderate 0.70 23 strong 0.75 14th moderate 0.10 1.00 ¹ 24 ¹ no 2.05 102 ¹ traces

309819 / 115S

BATH ORIGINAL

Additive GoY. '. Jo Ternp. Initial AiIZ Initial AKV, 3chJbiiüh- Example additive ° G K /, KV, cSt Ji. Ml-

2 219 Oj 13 0.87 28.00 '. 11 inUßi £ -

1 1.23 '11 spools

2 232 0.13 4.03 28.00 ^Ί 5G moderate

1 6.06 .γ 123 lanes

2 219 O ₅ 13 1.23 '~ 27' 70 20 tracks

1 3 ", 26-45 easy

2,232, 0.13. 6.03 27.70 117 n & ßifc

1 - '7.56 114 tracks

2 219 0.13 0.69 '27 \ C9 10 easy

1 3.06 42 easy

2 232 0.13 ■ 4.03 27.09 86 loiolrfc 1 ■ "5.56 109 light

1Ü 2 219 0.13 0 _} 69 25.87 17 3 ei tat

1 3.76 67 tracks

2 232 0.13 4,? 3 25.87 '.98 easy 1 A, 56 117 easy

Vj 2 219 0.05 0.97 -26.85 28 koine

1 0.74 19 coins

2 232 0.05 1.77 2ö, £> / i 56 none 1 2.48 60 none

2 219 0.05 1 _r ? 7 26.94 30 none 1 0.93 ■ 17 none 2.232 0.03 1.97 53 l: e: inc 1. 5.08 52 ■ none

2,219 0.05 0.73 25.59 '29 koino 1 0.74 23 none

"2 232 0.05 2.47 25.47 67 none

1 3.58 C> 7 Ir. C ine

2 232 0.25 1.63 26.52 51 'none 1 3.47 78 none

2 232 0.13 2, - 'i5 27.33 54 line 1 2.46 47 none

3098 19/1155

BATHROOM 0RK31NAL

Additive
example Ge \ f.%
Additive Temp. Initial
NZ ... 0.1 Λ NZ At first-
KV, casst
b.37.8 ° C Δ KV, Mud-
Ml-
manure 24 2 219 0.13 5.23 26.88 74 traces 1 1.96 34 easy 2 232 0.13 7.1 ,. 27.41 152 no 1 4.97 J 147 kelno 25th 2 219 0.13 0.94 " " ^ 28.60 13th no 1 0.97 9 no 2 232 0.13 2> 74 23.86 42 no 1 - 3.57 80 no 27 2 219 0 1.3 27.69 23 strong 1 0.8 27.69 17th ■ strong 0.3 1.1 26.62 18th strong 0.23 0.8 26.62 20th ßar-k 2 219 1.5 28.01 27 strong 1 0.4 28.01 14th strong 0.5 0.7 26.96 15th strong 0.25 0.7 26.96 19th star];

genci) at2-;

The hi or .in teGo-level prefixes can be used in conjunction with other tk: hiaioriVjittol additives. In the case of a golf course, their own characteristics are not adversely affected. The other additives Kgs NEN bc'if'.pj.olKvio.-i.FO anclei'-e Λ-r'J okyclaritj.cn be v / ie .Amino, Lautt. T'af;'N.-'- , ^c ; with "'; el _f Mcitall-i'. 'ii'.pprcfjiioren and the like. The following- ·

3 O 9 8 1 9/1 1 5 p

BATH ORIGINAL

The table below shows the results obtained when combinations of alkoxydiarylamines and other amines were used. In all cases the same lubricant was used as above. All tests were performed at 232 C (45O ⁰ F). 1 Ge / i.% Of the two additives was used in each case.

Additive

E.g
E.g
E.g

2 + DODPA
2

At first-
NZ • ΔΝΖ At first-
KV, cSt
b.37.8 ° C Λ KV,
% mud
education 0.1 2.25 26.73 60 no 0.05 3.45 27.90 69 traces 0.1 3.40 28.10 9 easy 0.1 1.10 29.98 1 easy 0.1 ι;? ö 27.18 56 no 0.1 2.45 27.41 71 traces 0.13 1.93 27.82 66 no

4 + PAN

9 + DODPA
Ex. 13 + DODPA
E.g. 21 + PAN
E.g. 23 + PAN
E.g. 23 + DODPA

Dioctyldiphenylamine

N-phenyl-1-naphthylanine

When using combinations of additives, the alkoxy diarylamines and diarylamines can be present in proportions which can vary from about 1 to 4: 4 to 1. They are preferably in a ratio of 1: 1. The total amount of the additive mixture should, however, be within the range given above for the alkoxydiarylamine additive alone, ie in the range from about 0.005 to about 10% by weight, preferably from about 0.1 to about 5% by weight , based on the lubricant .

In addition to the specific, in combination with the invention Älkoxydiarylaminen shown diarylamines · can other amines such as phenyl-1- or -2-naphthylamine and dinaphthylamine be used. The suitable diarylamines

309819/1 155

■ - -1 / f -

can through the general formula

R _x - Ar - NH - Ar ¹ - R

where Ar and Ar ¹ are independently selected from the group consisting of phenyl and naphthyl, R and R ^{1 are} hydrogen or C 1-4 alkyl, and χ and y are 0 up to the appropriate positions on the ring .

309819/1155

Claims (1)

Claims 1. Lubricant mixture containing a lubricant base and an arylamine antioxidant., thereby g e k e η η draw t that the arylamine antioxidant is the general Formula ' where Ar and Ar ¹ denote phenyl, naphthyly anthryl and / or phenanthryl, R and R ¹ denote benzyl groups or alkyl groups with 1 to 20 carbon atoms and ia and η are 0 to 5, at least one of these numbers being at least 1 is. Schiraerffilttelgemisch for "" in claim 1, characterized GEK e η η η η et verifiable that the arylamine AntioX3 ^r da3.is in the Sclmiiermlttelgemisch in amounts of O to ₅ OO5 iO wt.% Of the lubricant is present. 3. Lubricant mixture according to claim 1 or 2, characterized characterized in that the arylamine antioxidant 3-octoxydiphenylin is. 4. Lubricant mixture according to claim 1 or 2, characterized in that the arylamine antioxidant is 4.4 ^t -diisopentoxydiphenylamine, 5. Shear agent mixture according to claim 1 or 2, characterized characterized in that the Arylamii-i-antioxidant Is 3-octoxy-4-tert-octyldiphenylamine. 6. Lubricant mixture according to claim 1 or 2, characterized g e k e η η ζ e i c Ii η e t that the ArylamJ n-antioxidant 4 ~ Octo: x: yphenyl-1-naphthylamine I st * 309819/1155 7. Schmlermittelgcrnisch according to claim 1 or 2, characterized characterized in that dar; Arylamine antioxidant Is N-phenyl-1 - (4-octoxy) naphthylamine. 8?) Method of making compounds of general formula -V (RO) _m ~ f-Ar-] MTI E ~ Ar '-] (OR _n wherein where Ar and Ar 'are phenyl, naphthyl, anthryl and / or. or Phe ·; - anthryl, II and R ^{1 are} benzyl groups / ocier alkyl groups with 1 bin · 20 carbon atoms and m and η are 0 to fj, at least one of these numbers being at least 1, characterized in that one is an aminopkenol with an alkyl balogenide in the presence of an alkali metal carbonate in dimethyl sulfoxide, acet / nitrile or a dialkyl formamide as solvent. 9. traversing one according to Claim 8, characterized in that a ratio of halide to aminophenol alkylene of 1: employing 1: 1 to 1.5. 10. The method according to claim 8 or 9, characterized in that g e k e η η-draws that one the aminophenol and the alkali metal carbonate in the ratio of 1 to 10 equivalents of carbonate per equivalent of aminophenol. 309819/1155